JP4517450B2 - Polyester composition, film comprising the same, and magnetic recording medium - Google Patents

Description

【０１０３】
【発明の効果】
本発明は、優れた表面性、易滑性、耐熱性を有し、従来の添加物による方法では成形時あるいは加工時のブリードアウトなどで製品品位や成形工程，加工工程の汚染あるいは経時変化による種々の問題を解決することができる。
【０１０４】
本発明の組成物は、その優れた特性から繊維、シート、フィルム、成形材として種々の形態に加工し、適用できる他、特にフィルムとすることにより優れた効果を発現し、本発明のフィルムは上記した磁気記録媒体、特に蒸着型磁気記録媒体に好適に用いることができ、この他、インクリボン用ベースフィルムや飲用缶や建材などの金属板の貼り合わせ用途、電気機器の外装材、コンデンサー用、電子部材のキャリアーフィルム、ガラス部材への貼り合わせ用途、感熱孔版印刷用途などをはじめとした種々の一般工業用途にもちいることができる。また、加工特性にも優れており、製品歩留まりとしても優れている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester composition having excellent surface properties, slipperiness and heat resistance, and particularly suitable for use in a base film for a magnetic recording medium.
[0002]
[Prior art]
Conventionally, polyesters typified by polyethylene terephthalate have been widely used as fibers, films, and other molded articles because they have excellent physical and chemical properties. Among these molded products, films are used for magnetic recording media, capacitors, food packaging, heat-sensitive stencil printing, and other general industrial applications, etc. to improve the handleability and various performances of processed products. Various additives are used for the purpose.
[0003]
Moreover, adding moderate particle | grains in order to form moderate unevenness | corrugation on the surface of a film, and to provide slipperiness and abrasion resistance is performed.
[0004]
As such additives, for example, polyolefins, higher fatty acids, fatty acid esters and the like have been used for a long time to impart lubricity. For example, JP-A-56-109245, JP-A-57- Japanese Patent Application Laid-Open Nos. 27777, 58-24848, 62-179557, and the like are known.
[0005]
[Problems to be solved by the invention]
However, since such an additive is contained as a component independent of the polyester, the compatibility state may be a problem. When the compatibility state is poor, for example, when it is formed into a stretched film, it is depressed or coarse. The surface condition deteriorates. Even if the compatibility state is good, the additive component bleeds out during molding, processing, or over time, and the surface properties may be impaired, the processing process may be hindered, dyeing or coating The higher-order processing steps such as the above are made difficult, and the quality is changed to deteriorate the stability.
[0006]
The present invention solves this problem, particularly focusing on easy slipping, has excellent slipperiness, has excellent surface properties, and has excellent heat resistance, and a polyester composition and film and magnetic recording medium It is intended to provide use as a base film.
[0007]
[Means for Solving the Problems]
Such an object of the present invention is toContains at least one compound selected from aliphatic (mono or poly) alcohols, aliphatic (mono or poly) carboxylic acids, and those to which these functional groups are bonded.A polyester composition composed of polyester, which is obtained by dividing a peak area in the range of 1 to 3 ppm when observed by hydrogen nucleus NMR by a peak area in the range of 4 to 6 ppm as a peak ratio A. What is obtained by dividing the peak area in the range of 1 to 3 ppm by the peak area in the range of 4 to 6 ppm when the polyester composition obtained by dissolving in a solvent, diluting with toluene and reprecipitating is observed by hydrogen nucleus NMR When the peak ratio B is set, the peak ratio B is 15 × 10^-3300 × 10 or more^-3This is achieved by a polyester composition characterized in that the peak ratio B / peak ratio A is 0.7 or more, or a film obtained from the composition.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the polyester used in the present invention include those composed of a dicarboxylic acid component and a glycol component, such as an esterification or transesterification reaction of a dicarboxylic acid or an ester-forming derivative thereof with glycol and a subsequent polycondensation reaction. The
[0009]
The type of polyester is not particularly limited as long as it can be formed into a molded article such as a film. Suitable polyesters that can be formed into molded articles such as films are those using aromatic dicarboxylic acid as the dicarboxylic acid component, such as polyethylene terephthalate, polyethylene-p-oxybenzoate, polyethylene-1,2-bis ( 2-chlorophenoxy) ethane-4,4'-dicarboxylate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, polyethylene-2,6-naphthalenedicarboxylate, polybutylene Examples include terephthalate, polycyclohexane-1,4-dimethylene terephthalate, and among them, polyethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, polybutylene terephthalate, and poly-1,3-trimethylene terephthalate are preferable. These copolymers or blends are also a preferred embodiment.
[0010]
Of course, these polyesters may be copolyesters. Examples of the copolymer component include acid components such as aromatic dicarboxylic acid, aliphatic dicarboxylic acid and alicyclic dicarboxylic acid other than acid component and glycol component constituting the above-mentioned polyester, aromatic glycol, aliphatic glycol and alicyclic Glycol components such as glycol may be copolymerized. Examples of such components include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phthalic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, and 5-sodium. Aromatic dicarboxylic acids such as sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, decalin dicarboxylic acid, etc. Alicyclic dicarboxylic acid It can be mentioned.
[0011]
As glycol components, ethylene glycol, 1,3-trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, diethylene glycol, 1,6-hexanediol, 1,10-decanediol And alicyclic glycols such as 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and hydrogenated bisphenol A. Among these glycol components, ethylene glycol, 1,3-trimethylene glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferably employed.
[0012]
In addition, the above-mentioned acid component and glycol component may be used alone or in combination of two or more. Further, these copolymer components may be by-produced when the polyester is produced.
[0013]
In the present invention, the amount of carboxy end groups in the polyester composition is preferably 10 to 100 equivalents / ton. The lower limit is preferably 12 equivalents / ton, more preferably 15 equivalents / ton. The upper limit is preferably 80 equivalents / ton, more preferably 70 equivalents / ton. By setting it as such a range, heat resistance will become favorable and it will work effectively also in moldability.
[0014]
Polyester of the present inventionConsist ofThe polyester composition is an embodiment in which a component other than the polyester component, for example, a component that forms a peak in the range of 1 to 3 ppm when observed by hydrogen nucleus NMR described later is combined with the polyester, that is, a small amount of different components. It means that it may be included.
[0015]
Next, the polyester composition of the present invention comprises a peak ratio A obtained by dividing a peak area in the range of 1 to 3 ppm by a peak area in the range of 4 to 6 ppm as observed by hydrogen nucleus NMR, and the polyester composition once. Peaks in the range of 1 to 3 ppm when a polyester composition obtained by dissolving in a solvent that dissolves a polyester composition such as orthochlorophenol or hexafluoroisopropanol, diluting with toluene and reprecipitating is observed by hydrogen nucleus NMR. The peak ratio B obtained by dividing the area by the peak area in the range of 4 to 6 ppm needs to satisfy specific requirements.
[0016]
That is, the peak ratio B is15× 10^-3more than,300× 10^-3The peak ratio B / peak ratio A needs to be 0.7 or more.
[0017]
The lower limit of peak ratio B is15 × 10^-3And the upper limitIs 300x10^-3It is. Below this range, the improvement of the slipperiness is not sufficient, and at the same time, the effect is not particularly expected, and the moldability and heat resistance deteriorate. Especially 15 × 10^-3The above is preferable because moldability is good and film formation at high speed is easy.
[0018]
Further, the peak ratio A is not particularly limited, but the lower limit is preferably 5 × 10.^-3, More preferably 10 × 10^-3The upper limit is preferably 600 × 10^-3, More preferably 500 × 10^-3, More preferably 400 × 10^-3It is. By setting it as such a range, it can be set as the film excellent in slipperiness and heat resistance.
[0019]
The value obtained by dividing the peak ratio B by the peak ratio A is more preferably 0.8 or more, still more preferably 0.9 or more, and particularly preferably 0.95 or more. The upper limit is not particularly limited but is preferably about 1.0. By adopting such a range, there is no bleed out even in a long thermal history, especially when used as a magnetic recording medium, the formation of coarse protrusions on the magnetic layer surface is suppressed, and the heat resistance is also good and excellent. A film having characteristics can be obtained.
[0020]
In addition, about the measuring method of hydrogen nucleus NMR, it explains in full detail in the following Example.
[0021]
In addition, when the polyester composition is dissolved in a solvent, if there is an insoluble matter other than the polyester composition, it may be filtered. In the present invention, toluene is used as the reprecipitation solvent. This is for separating and concentrating the components. When the components other than the polyester precipitate simultaneously, the reprecipitation solvent is changed, or the reprecipitation component is washed with another solvent that does not dissolve the polyester component. Is equivalent to
[0022]
Usually, in hydrogen nucleus NMR, the peak in the range of 1 to 3 ppm is attributed to (cyclo) alkyl group, (cyclo) alkylene group, (cyclo) alkyne group, etc.Is oneIt is preferable that it originates in a valent alkyl group. In such a case, the slipping property is further improved.
[0023]
The mechanism of action of the present invention is not necessarily clear, but considering the compatibility and the change in free energy during crystal formation, the structure accumulates in the amorphous part of the polyester, and the domain with good slipperiness is extremely dispersed microscopically. It seems that it is because it is.
[0024]
As an analysis method for the composition of the peak component, it is possible to examine and analyze the NMR spectrum in detail. For example, after the polyester composition component is subjected to a solvolysis step such as methanolysis, It is also possible to fractionate and obtain components by making full use of analytical methods such as chromatographs.
[0025]
In the present invention, when the polyester composition is subjected to thermogravimetric analysis in a nitrogen atmosphere at a temperature rising rate of 20 ° C./min, the thermogravimetric decrease is usually 0.3 to 300 ° C. before reaching the melting point. It is preferable that it is below wt%. More preferably, it is 0.2 weight% or less, More preferably, it is 0.15 weight% or less, Most preferably, it is 0.1 weight% or less. Although the lower limit is not particularly defined, it is about 0.03% by weight. Polyester compositions are often molded under melting, but when these conditions are satisfied, the processability is excellent and the quality of the product is improved. Also, it can withstand long-time film formation and has excellent productivity.
[0026]
Moreover, in this invention, it is a preferable aspect to contain an inert particle for the further improvement of slipperiness, and a synergistic effect | action is acquired. The inert particles referred to here are particles that are incompatible with polyester even at a part thereof.
[0027]
The inert particles contained in the present invention are not particularly limited as long as the final composition satisfies the requirements of the present invention, but silicon, aluminum, zinc, iron, titanium, zirconium, molybdenum, cerium, yttrium, tin, Inorganic particles such as barium, calcium, magnesium, sodium, potassium, oxides, sulfides, sulfates, nitrates, halides, carbonates, phosphates, styrene derivatives, (meth) acrylic acid derivatives, chlorinated vinyl Examples thereof include organic particles containing vinyl resins such as derivatives and vinyl alcohol derivatives, fluorine resins, and silicone resins as constituent components. Among them, silicon, aluminum, zirconium oxide, styrene-based resin, and silicone resin can be obtained that have good sliding properties, wear resistance, and heat resistance. Moreover, it is preferable to use spherical particles, and it is preferable that the thermal loss at 350 ° C. is 1% by weight or less when thermogravimetric analysis is performed in a nitrogen atmosphere.
[0028]
Such inert particles are preferably used in an amount of 0.005 to 5% by weight in terms of slipperiness.
[0029]
Moreover, as an average particle diameter of an inert particle, 0.005-20 micrometers is preferable. The lower limit is preferably 0.1 μm, and more preferably 0.2 μm. The upper limit is preferably 15 μm, more preferably 10 μm, and particularly preferably 5 μm. The present invention can be suitably processed into a film, a sheet-like material, and the like, but if it has an average particle size equal to or greater than the lower limit, good characteristics in terms of slipperiness and wear resistance can be obtained. In addition, if it has an average particle size below the upper limit, the impact on the surface configuration when performing surface processing such as particle dropout and vapor deposition and coating of the coating in the processing step becomes minor, Yield and product quality will be good.
[0030]
In the present invention, it does not prevent the inclusion of two or more kinds of inert particles (including those having the same chemical composition and different average particle diameters), but rather has better wear resistance and slipperiness. Since it can be used, it is preferably adopted.
[0031]
Next, embodiments of the present invention will be specifically described using examples, but the present invention is not limited to such descriptions.
[0032]
For the synthesis of the polyester, for example, a so-called transesterification method using a dialkyl ester of an aromatic dicarboxylic acid and ethylene glycol or a direct polymerization method in which the dicarboxylic acid and ethylene glycol are directly reacted is preferably employed.
[0033]
Known catalysts can be used, for example, an alkali metal acetate is used as the transesterification catalyst, and an antimony oxide catalyst with less contamination such as germanium oxide or bismuth can be used as the polymerization reaction catalyst. Among them, it is preferable to employ a germanium oxide catalyst. Moreover, combined use, such as transition metal compounds, such as cobalt, and an alkoxy titanate, can be employ | adopted preferably.
[0034]
In addition, phosphorus compounds such as trialkyl phosphates, monoalkyl phosphates, phosphoric acid, phosphorous acid, dialkylaryl phosphonates, carboalkoxyalkenyl dialkyl phosphonates are preferably blended for the purpose of improving heat resistance. Can do.
[0035]
Next, in order to obtain the polyester composition of the present invention, a peak at 1 to 3 ppm is observed in the reaction step when the functional group having a reactive activity on the carboxyl group or hydroxyl group constituting the polyester and hydrogen nucleus NMR is observed. It is effective to react a compound to which a component that expresses is bound.
[0036]
like thisAs the compound, from the viewpoint of moldability and heat resistance, aliphatic (mono or poly) alcohol, aliphatic (mono or poly) carboxylic acid and those having these functional groups bonded can be used.
[0037]
The number of carbon atoms in the aliphatic moiety, that is, the (cyclo) alkyl group, (cyclo) alkene group, (cyclo) alkyne group) is preferably 8-30, and the lower limit is preferably 10, more preferably 12. Particularly preferably 14, the upper limit is 26, more preferably 24, and particularly preferably 20. When the above compounds are used, the number of carbon atoms becomes a factor that affects the compounding force on the polyester part, the molecular weight, and the polymerization reactivity. By setting the above range, the moldability and slipperiness are sufficient, and the heat resistance It is possible to obtain a polyester composition having good properties and mechanical properties.
[0038]
Moreover, when using a compound as described above, the vapor pressure at 200 ° C. is preferably 200 Pa or less, more preferably 100 Pa or less, and particularly preferably 50 Pa or less. The lower limit is not particularly limited, but it is practical if it is about 0.01 Pa from the viewpoint of handleability.
[0039]
In addition, when using a compound as described above, the timing of its addition is important along with the design of the reaction system. In the present invention, for example, when the polyester is polyethylene terephthalate, the intrinsic viscosity is preferably added between 0.05 and 0.8. The lower limit is more preferably 0.1, still more preferably 0.3, particularly preferably 0.4, and the upper limit is more preferably 0.7, still more preferably 0.65. If the addition time is late, the degree of polymerization is difficult to increase, the moldability and mechanical properties are liable to be impaired, and the reprecipitated polyester does not remain, and the effects of the present invention cannot be sufficiently obtained. May precipitate when heated, and the effects of the invention may not be sufficiently obtained, or the process may be fouled during molding or processing into a film or the like, thereby impairing productivity. On the other hand, if the addition time is too early, low molecular weight substances are likely to be produced, and it becomes difficult to obtain the effect of the invention by bleeding out when heated, or the process is fouled during molding or processing on a film or the like. For this reason, productivity may be impaired. Even in the case of other polyesters, the addition time may be appropriately adjusted to obtain the polyester composition of the present invention.
[0040]
In addition, it is preferable to add the compound once by filtration through a filter, and as the filter, use a filter that does not filter foreign matters of 2 μm or more, or can cut 90% or more of foreign matters of 1 μm or more. Is preferred. When the filter is used, the surface property is very good, and the application to an evaporation type magnetic recording medium described later is extremely suitable.
[0041]
It is preferable to continue the polymerization reaction again after the addition, to obtain a preferable intrinsic viscosity, and to sufficiently disperse or react the above-described compound in the polyester, so that the final polyester composition can be prepared. it can.
[0042]
The polyester composition of the present invention has an intrinsic viscosity of preferably 0.45 g / dl or more, more preferably 0.5 g / dl or more, and particularly preferably 0.55 g / dl or more. The upper limit is not particularly limited, but is about 1.2 g / dl from the viewpoint of workability. By making it into this range, the moldability can be further improved.
[0043]
In addition, when the particles are included, the method is not particularly limited, and the slurry is injected into a uniaxial or biaxial kneader equipped with a vent port before polymerization or during the polymerization process or after polymerization. Or a method of mixing a separately prepared particle-containing polyester composition under melting, a method of adding during the polymerization step or a method of mixing a separately prepared particle-containing polyester composition under melting. Is preferable because it can be carried out easily.
[0044]
The polyester composition of the present invention thus prepared can be molded by a known method. For example, a specific method for producing a film comprising the polyester composition of the present invention will be described. After drying, the polyester composition is melt extruded to form an unstretched sheet, followed by biaxial stretching and heat treatment to form a film. A method is mentioned. Biaxial stretching may be longitudinal, lateral sequential stretching, or biaxial simultaneous stretching. The draw ratio is usually appropriately 2.0 to 5.0 times in the vertical and horizontal directions. Further, after biaxial stretching, the film may be re-stretched in either the longitudinal or transverse direction. Moreover, each particle raw material containing polyester and the polyester resin which does not contain particle | grains can be mixed suitably, and the mixing | blending of an inert particle can be measured. As the stretching condition, a mode in which stretching is performed at a low temperature of Tg + 100 ° C. or less or at a speed of 2000% / min or more is preferably employed.
[0045]
When implementing the present invention as a laminated film, for example, preparing a plurality of feeders and extruders, charging and melting each raw material, obtained by laminating and extruding using pinol or the like at the time of melt molding, After the formation of one layer, it can be cast and molded thereon. In the former case, the lamination thickness can be adjusted by making the melt viscosity of the raw materials as equal as possible and controlling the amount of extrusion from each extruder. It is important that the polyester composition of the present invention is used in at least one outermost layer from the functional side.
[0046]
The thickness unevenness with respect to the total film thickness of the film of the present invention is preferably 20% or less, more preferably 14% or less, and further preferably 10% or less. The lower limit is not particularly limited, but is about 2% from the viewpoint of productivity. When the thickness unevenness exceeds 20%, the quality as a molded product is inferior, and there is a concern that workability and flatness deteriorate.
[0047]
In addition, the film of the present invention has 20 defects / mm of depressions with an equivalent circle diameter of 1 μm or more on the surface on the side containing the composition of the present invention.²Preferably, the number is 10 / mm²More preferably, it is 5 or less / mm.²More preferably, it is as follows. When different components are contained, the deformability under stretching stress is different, so that depressions or protrusions are often formed. In the structure of the present invention, since there are many combinations of the additive and the polyester, it can be preferably suppressed, a fine surface is formed, and a film particularly suitable for a vapor deposition tape can be obtained. The lower limit is not particularly defined, but it is preferable that such a depressed defect is not formed.
[0048]
In addition, the polyester composition of the present invention and the film comprising the same may have other thermoplastic resins, such as polyethylene, polypropylene, polystyrene, and the like, and various additives such as carbodiimide, epoxy compounds, etc., as long as the object is not impaired. A blocking agent, ultraviolet absorber, antioxidant, antistatic agent, surfactant, pigment, fluorescent whitening agent, and the like may be contained.
[0049]
Moreover, a coating layer can be formed in the film of this invention as needed. Forming the coating layer includes a method of forming at an arbitrary point in the film formation process or off-line after film formation, but coating is performed at the time of film formation because there is little concern that scratches will be generated and productivity is good. Is preferred. For example, a method of applying a coating agent using a metalling bar or a gravure coater after casting / stretching and simultaneously performing drying / stretching can be mentioned.
[0050]
The coating agent may be prepared by a known method. The refractive index of the coating composition is affected by the composition of the coating, the drying conditions, the stretching conditions, etc. As the composition, it is easy to use a cross-linked acrylic or urethane coating agent with a flexible adjustment range. .
[0051]
Next, when obtaining a magnetic recording medium, a solution of a binder resin such as urethane or acrylic containing magnetic powder such as Co, Ni, or ferrite is applied to at least one surface of the film, dried, and calendered. A method of forming a resin layer containing a lubricant (coating-type magnetic recording medium), forming a magnetic metal thin film layer by depositing magnetic metal on at least one surface of the film, and further forming a protective layer and a lubricating layer if necessary. There is a method (evaporation type magnetic recording medium) in which an easy-sliding layer is provided on the surface opposite to the surface on which the magnetic surface is formed. In the case of a tape, it can be obtained by cutting into a tape shape. In the present invention, since excellent slipperiness and surface properties are simultaneously provided, high surface accuracy is required, and it can be preferably used for a vapor deposition type magnetic recording medium suitable for high density recording.
[0052]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
The measuring method of the characteristic value in the present invention was performed by the following method.
[0053]
A. Average particle diameter
The cross section of the polyester composition is observed with a transmission electron microscope (TEM) at a magnification of 10,000 times or more. The section thickness of TEM is about 100 nm, and the measurement is performed at 100 fields or more at different locations. The average diameter d of the particles is obtained as an equivalent circle equivalent diameter.
[0054]
B. Particle content
The polyester composition is dissolved in orthochlorophenol, and the insoluble matter is separated using a centrifuge. The separated product was washed and dried to obtain a constant weight, which was then determined as a weighed value.
[0055]
C. Peak ratio
The polyester composition was freeze-pulverized to form a powder, dissolved in a mixed solvent of hexaisopropanol and deuterated chloroform, and determined with an H-NMR measuring instrument (GSX-400) manufactured by JEOL Ltd. (peak ratio A). .
[0056]
On the other hand, the polyester composition is dissolved in hexafluoroisopropanol (HFIP), and first, insoluble matters are filtered off. Subsequently, toluene was gradually added to the filtrate, and when the required amount of polymer precipitate was observed, the addition was stopped and the filtrate was filtered off. The filtrate was washed several times with a methanol / HFIP mixed solvent and then methanol and dried. After drying, the sample was measured by the same method as the above peak ratio A to obtain the peak ratio (peak ratio B).
[0057]
In calculating the peak ratio, the peak corresponding to the solvent and impurities was subtracted.
[0058]
D. Analysis of solvolysis products
The polyester composition was subjected to methanolysis using methanol, and the components were separated by a high performance liquid chromatograph, and the structure and weight of each separated product were determined and calculated.
[0059]
E. Thermal weight reduction
Weigh the sample and use a thermogravimetric analyzer (TGA-50) manufactured by Shimadzu Corporation to raise the temperature from room temperature to 350 ° C. in a nitrogen atmosphere at a temperature rising rate of 20 ° C./min. The heat loss at 300 ° C. was determined by setting the 200 ° C. time as the zero point.
[0060]
F. Intrinsic viscosity of polyester composition
Measurement was performed at a measurement temperature of 25 ° C. using o-chlorophenol as a solvent and an Oswald viscometer.
[0061]
On the other hand, the intrinsic viscosity at the time of addition was determined by preparing a calibration curve between the stirring torque and the intrinsic viscosity and converting from the stirring torque.
[0062]
G. Carboxy end group amount
The polymer was dissolved in a mixed solvent of ortho-cresol / chloroform (weight ratio 7: 3) at 90 to 100 ° C. and determined by potentiometric titration using an alkali.
[0063]
H. Thickness unevenness of film
Measure the thickness at least 500 points arbitrarily sampled from the film roll,
(Maximum thickness-minimum thickness) / average thickness x 100 (%)
Determined by
[0064]
I. Film thickness
The distribution of particle concentration in the depth direction is measured with a secondary ion mass spectrometer, X-ray photoelectron spectroscopy, infrared analysis, or confocal microscope. After obtaining the maximum value in the depth direction with the surface as a reference, the depth that is 1/2 of the maximum value was defined as the laminated thickness. In addition, when the lamination thickness is small, it can be determined not only from the depth distribution of the particle concentration but also by observing the cross section of the film or by a thin film level difference measuring device.
[0065]
J. et al. The number of depressions
Aluminum was vapor-deposited on the obtained film, the surface was observed with a differential interference microscope, the field was counted for 10 points, and the average value was obtained.
[0066]
K. Film slipperiness
The dynamic friction coefficient was obtained. The dynamic friction coefficient (μk) is SUS420J having an outer diameter of 8 mmφ and a surface roughness of 0.2 S in an atmosphere of 25 ° C. and 50% RH using a dynamic friction coefficient device (TBT-300) manufactured by Yokohama Seisakusho. After making contact at a winding angle of 180 degrees and moving at a speed of 3.3 cm / sec, the tension is controlled so that the entry side tension T1 is 25 g, and the following formula is obtained from the value of the exit side tension T2 (g).
μk = (2 / π) ln (T2 / T1)
Determined by
[0067]
L. Blocking
The roll film 10000 m was rewound under vacuum, then opened to the atmosphere, then placed in an atmosphere of 25 ° C. and 60% RH for 6 days, and then unwound at a speed of 140 m / min. The behavior of the film at that time was judged according to the following criteria.
No film accompaniment is seen: ◎
The film is drawn slightly, but there is no change in the roll shape after unwinding
: ○
The film is attracted, and the roll shape after unwinding is deteriorated
: △
Tearing occurs as the film draws along: x.
[0068]
M.M. Number of dropouts
Using a continuous vacuum deposition apparatus on the film surface, a deposited layer of cobalt-nickel alloy (Ni 20 wt%) was formed (200 nm) in the presence of a small amount of oxygen. Next, a carbon protective film and a fluorosurfactant were applied to the surface of the vapor deposition layer, a back coat layer was provided on the opposite side, and then cut to 8 mm width to prepare a pancake. Next, a length of 200 m from this pancake was incorporated into a cassette tape.
[0069]
The cassette tape was evaluated using a commercially available Hi8 VTR. A 4.4 MHz signal was supplied from the TV test signal generator, and the number of dropouts with a reproduction signal attenuation of -16 dB or more and a length of 15 μsec or more was determined using a dropout counter. The number of dropouts after 100 times of regeneration / rewinding for 3 minutes at 25 ° C. and 65% RH was converted to the number per minute and judged as follows.
0-15 pieces / minute: ◎
16-30 pieces / min: ○
31-pieces / minute: x.
[0070]
Filtration work
Each of commercially available stearyl stearate, decalyl decalate, and behenyl behenate was melted and passed through a 2 μm, 100% cut pleated filter to prepare each filtered product.
[0071]
Example 1
Transesterification was performed according to a conventional method using 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol using 0.09 part by weight of lithium acetate as a catalyst.
[0072]
Thereafter, 0.08 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate as a phosphorus compound were added, followed by a polycondensation reaction according to a conventional method, and when the intrinsic viscosity reached 0.5 g / dl, Once the pressure was returned to normal pressure, stearyl stearate was added to 2% by weight per polymer weight, stirred for 5 minutes and then decompressed again to continue the polycondensation reaction. The obtained polyester composition had an intrinsic viscosity of 0.60 g / dl, a carboxyl end group amount of 30.2 equivalent / ton, a peak ratio A and a peak ratio B of 78 × 10.^-374 × 10^-3The thermal weight loss was 0.08% by weight (Polyester A).
[0073]
Further, after the transesterification reaction, an ethylene glycol slurry of 20 wt% colloidal silica having an average particle diameter of 0.3 μm (manufactured by Catalyst Kasei Kogyo Co., Ltd.) was added as 2 wt% with respect to the polyester resin. A slippery polyester composition was obtained (polyester B) using the same preparation method as polyester A except that no rate was added.
[0074]
Moreover, the polyester composition for dilution was obtained using the preparation method similar to the said polyester A except not adding a stearyl stearate (polyester C).
[0075]
Next, each of polyesters A, B, and C is sufficiently dried, mixed so that polyester A / polyester B / polyester C = 25/10/65, supplied to an extruder, melted at 285 ° C., and T-type The film was extruded from the die into a sheet and cooled and solidified with a cooling drum at 30 ° C. to obtain an unstretched film. Next, the unstretched film was stretched simultaneously at 100 ° C. in the longitudinal direction at 3.0 times and in the transverse direction at 3.0 times, and then heat-treated at 200 ° C. to obtain a film having a total thickness of 7.5 μm. The characteristics of the obtained polyester film are shown in Table 1.
[0076]
Next, 100 parts of Co powder, 15 parts by weight of polyurethane resin, 5 parts of vinyl chloride / vinyl acetate copolymer resin, 5 parts of nitrocellulose resin, aluminum oxide powder (average diameter 0.3 μm) 3 on one surface of the film Part, 100 parts of methylethylke, 100 parts of toluene, and 2 parts of stearic acid were applied, dried and heat cured, and then a back coat layer containing carbon black and a thermosetting urethane resin was formed on the back surface. And slitting to obtain a magnetic tape. The film had good sliding properties and good properties as electromagnetic conversion characteristics.
[0077]
Example 2
Prepare two extruders, one layer is polyester A, polyester B, and polyester C used in Example 1 above, and the other layer is polyester C with a final film thickness of 1.5 μm and 6 μm, respectively. Then, a film was obtained in the same manner as in Example 1.
[0078]
Subsequently, a water-soluble coating layer consisting of a water-soluble polyester resin, a silane coupling agent, 20 nm colloidal silica particles, and carboxymethyl cellulose was applied to the film surface side consisting only of the polyester C layer and dried to obtain a film.
[0079]
Next, the film roll was placed in a vacuum deposition machine, and a Co—Ni film was formed on the coating layer surface side. Further, a protective layer (diamond carbon film) and a lubricating layer were formed on the vapor deposition surface by a known method. On the other side, a back coat layer containing carbon black and a thermosetting urethane resin was formed and slit to obtain a magnetic tape. The obtained results are shown in Table 1.
[0080]
Example 3
Polyester A was prepared in the same manner as in Example 1, except that stearyl stearate was added when the intrinsic viscosity in the system reached 0.35 g / dl.
[0081]
Next, a film and a magnetic tape were obtained in the same manner as in Example 2. The obtained results are shown in Table 1.
[0082]
Example 4
Polyester A was prepared in the same manner as in Example 1, except that stearyl stearate was added when the intrinsic viscosity in the system reached 0.1 g / dl.
[0083]
Next, a film and a magnetic tape were obtained in the same manner as in Example 2. The obtained results are shown in Table 1.
[0084]
Example 5
Polyester A was prepared in the same manner as in Example 1 except that decalyl decalate was used instead of stearyl stearate.
[0085]
Next, a film and a magnetic tape were obtained in the same manner as in Example 2. The obtained results are shown in Table 1.
[0086]
Example 6
Polyester A was prepared in the same manner as in Example 1 except that behenyl behenate was used instead of stearyl stearate.
[0087]
Next, a film and a magnetic tape were obtained in the same manner as in Example 2. The obtained results are shown in Table 1.
[0088]
Example 7
Dimethyl 2,6-naphthalenedicarboxylate was used instead of dimethyl terephthalate, the amount of addition was determined based on the molar ratio, and stearyl stearate was added as 1% by weight per polymer when the intrinsic viscosity was 0.6. Polyester A was prepared in the same manner as in Example 1.
[0089]
Next, a film and a magnetic tape were obtained in the same manner as in Example 2. The obtained results are shown in Table 1.
[0090]
Comparative Example 1
Prepare two extruders, with one layer containing polyester B and polyester C used in Example 1 above, and the other layer containing polyester C as the final film thicknesses of 1.5 μm and 6 μm, respectively. A film was obtained in the same manner as in Example 1 below.
[0091]
Next, a film and a magnetic tape were obtained in the same manner as in Example 2. The obtained results are shown in Table 1.
[0092]
Comparative Example 2
A transesterification reaction was carried out in accordance with a conventional method using 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol using 0.09 part by weight of lithium acetate as a catalyst.
[0093]
Thereafter, 0.08 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate as a phosphorus compound were added, followed by a polycondensation reaction according to a conventional method, and when the intrinsic viscosity reached 0.67 g / dl, Once the pressure was returned to normal pressure, stearyl stearate was added as 1% by weight per polymer weight, stirred for 5 minutes, and then polycondensed again to prepare polyester A.
[0094]
Next, a film and a magnetic tape were obtained in the same manner as in Example 2. The obtained results are shown in Table 1.
[0095]
Comparative Example 3
Polyester A was prepared in the same manner as in Example 1 except that a commercially available polyethylene wax was used instead of stearyl stearate.
[0096]
Next, a film and a magnetic tape were obtained in the same manner as in Example 2. The obtained results are shown in Table 1.
[0097]
Comparative Example 4
A transesterification reaction was carried out in accordance with a conventional method using 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol using 0.09 part by weight of lithium acetate as a catalyst.
[0098]
Thereafter, 0.08 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate as a phosphorus compound were added, followed by a polycondensation reaction according to a conventional method, and when the intrinsic viscosity reached 0.80 g / dl, Once the pressure was returned to normal pressure, stearyl stearate was added to 2 wt% per polymer weight, and the mixture was stirred for 5 minutes to prepare polyester A.
[0099]
Next, a film and a magnetic tape were obtained in the same manner as in Example 2. The obtained results are shown in Table 1.
[0100]
Comparative Example 5
A transesterification reaction was carried out in accordance with a conventional method using 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol using 0.09 part by weight of lithium acetate as a catalyst.
[0101]
Thereafter, stearyl stearate was added so as to be 2% by weight per polymer weight, and after stirring for 5 minutes, 0.08 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate as a phosphorus compound were added. A polycondensation reaction was attempted according to the law. However, after a while from the start of polymerization, a rise in the liquid level was observed, and deposits were deposited in the reduced pressure system, and the polymerization could not be continued.
[0102]
[Table 1]

[0103]
【The invention's effect】
The present invention has excellent surface properties, slipperiness, and heat resistance. In the conventional method using additives, bleedout during molding or processing causes product quality, molding process, processing process contamination, or changes over time. Various problems can be solved.
[0104]
The composition of the present invention can be processed and applied in various forms as a fiber, sheet, film, or molding material because of its excellent characteristics, and in particular, the film of the present invention exhibits an excellent effect by making it a film. It can be suitably used for the above-mentioned magnetic recording media, in particular, vapor deposition type magnetic recording media. Besides this, it is used for bonding base plates for ink ribbons, metal plates such as drinking cans and building materials, exterior materials for electrical equipment, and capacitors. Also, it can be used for various general industrial applications including application of electronic members to carrier films, glass members, thermal stencil printing, and the like. In addition, it has excellent processing characteristics and is excellent in product yield.

Claims (9)

A polyester composition comprising a polyester containing at least one compound selected from an aliphatic (mono or poly) alcohol, an aliphatic (mono or poly) carboxylic acid, and a compound to which these functional groups are bonded , The peak ratio in the range of 1 to 3 ppm as observed by nuclear NMR divided by the peak area in the range of 4 to 6 ppm is used as the peak ratio A. The polyester composition is dissolved in a solvent, diluted with toluene, and re- When the peak ratio B is obtained by dividing the peak area in the range of 1 to 3 ppm by the peak area in the range of 4 to 6 ppm when the polyester composition obtained by precipitation is observed by hydrogen nucleus NMR, the peak ratio B is A polyester composition characterized by being 15 × 10 ⁻³ or more and 300 × 10 ⁻³ or less and having a peak ratio B / peak ratio A of 0.7 or more. The polyester composition according to claim 1, wherein the peak in the range of 1 to 3 ppm is attributed to a monovalent alkyl group. The thermogravimetric reduction amount in the range of 200 ° C to 300 ° C when the polyester composition is thermogravimetrically analyzed at a temperature rising rate of 20 ° C / min in a nitrogen atmosphere is 0.3% by weight or less. The polyester composition described. The polyester composition in any one of Claims 1-3 containing an inert particle. The polyester film obtained using the polyester composition in any one of Claims 1-4. A laminated polyester film comprising the polyester film according to claim 5 in at least one layer. The polyester film according to claim 5 or 6, wherein the number of depression defects having an equivalent circle diameter of 1 µm or more on the film surface is 20 pieces / mm ² or less. A magnetic recording medium comprising a magnetic recording layer provided on at least one side of the polyester film according to claim 5. The magnetic recording medium according to claim 8, wherein the magnetic recording layer is a magnetic metal thin film.