WO2000026903A1 - Film polyester stratifie a orientation biaxiale pour support d'enregistrement magnetique - Google Patents
Film polyester stratifie a orientation biaxiale pour support d'enregistrement magnetique Download PDFInfo
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- WO2000026903A1 WO2000026903A1 PCT/JP1999/006080 JP9906080W WO0026903A1 WO 2000026903 A1 WO2000026903 A1 WO 2000026903A1 JP 9906080 W JP9906080 W JP 9906080W WO 0026903 A1 WO0026903 A1 WO 0026903A1
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- layer
- film
- biaxially oriented
- compound
- polyester film
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
- G11B5/733—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer characterised by the addition of non-magnetic particles
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
- G11B5/739—Magnetic recording media substrates
- G11B5/73923—Organic polymer substrates
- G11B5/73927—Polyester substrates, e.g. polyethylene terephthalate
- G11B5/73935—Polyester substrates, e.g. polyethylene terephthalate characterised by roughness or surface features, e.g. by added particles
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
- G11B5/739—Magnetic recording media substrates
- G11B5/73923—Organic polymer substrates
- G11B5/73927—Polyester substrates, e.g. polyethylene terephthalate
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
- G11B5/739—Magnetic recording media substrates
- G11B5/73923—Organic polymer substrates
- G11B5/73927—Polyester substrates, e.g. polyethylene terephthalate
- G11B5/73929—Polyester substrates, e.g. polyethylene terephthalate comprising naphthalene ring compounds, e.g. polyethylene naphthalate substrates
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
- G11B5/739—Magnetic recording media substrates
- G11B5/73923—Organic polymer substrates
- G11B5/73927—Polyester substrates, e.g. polyethylene terephthalate
- G11B5/73931—Two or more layers, at least one layer being polyester
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/90—Magnetic feature
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/923—Physical dimension
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/923—Physical dimension
- Y10S428/924—Composite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/923—Physical dimension
- Y10S428/924—Composite
- Y10S428/926—Thickness of individual layer specified
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- the present invention relates to a biaxially oriented laminated polyester film for a magnetic recording medium, and more particularly, to a biaxially oriented laminated film which is excellent in running durability and electromagnetic conversion characteristics and is useful as a base film of a magnetic recording medium with extremely small aperture.
- polyester film Regarding polyester film.
- the present invention also relates to a biaxially oriented laminated polyester film which is excellent in dry heat deterioration property and precipitation foreign matter suppression property.
- Japanese Patent Application Laid-Open No. 54-47010 discloses a non-magnetic material layer on a first Co thin-film magnetic layer attached on a non-magnetic support.
- a magnetic recording medium in which a second Co thin-film magnetic layer having a thickness greater than the thickness of the first Co thin-film magnetic layer is disclosed via Japanese Patent Application Laid-Open No. 52-134 No. 706 discloses a perpendicular magnetic recording medium made of a C 0 —Cr alloy.
- the IEICE Technical Report MR 94-778 (1995-002) discloses high-density magnetic recording using an ultra-thin layer coated magnetic recording medium. ing.
- Magnetic recording media in which magnetic powder is mixed with an organic polymer binder and coated on a non-magnetic support
- a ferromagnetic metal thin film formed by a thin film forming means such as a ring or ion plating has a very small thickness of 0.2 or less.
- Also in the case of an ultra-thin layer coating type, a nonmagnetic underlayer is provided. Available in 13 m thickness and very thin.
- the surface state of the non-magnetic support greatly affects the surface properties of the magnetic layer.
- the surface state of the nonmagnetic support is directly expressed as irregularities on the surface of the magnetic layer (magnetic recording layer).
- the surface of the nonmagnetic support (base film) is as rough as possible.
- the surface of the non-magnetic support is required to be smooth from the viewpoint of electromagnetic conversion characteristics, while it is required to be rough from the viewpoint of handling properties and film cost.
- Japanese Patent Application Laid-Open No. 5-194772 discloses that a polyester film is connected to one surface.
- a primer layer for the magnetic layer which is composed of a continuous thin film, is coated, and the surface of the continuous thin film of the primer layer is (A) a height of 13 nm or less with a core having an average particle diameter of less than 0.06 as a core.
- C minute protrusions made of only a resin forming a single primer layer. The number of protrusions is
- AN is the number of small protrusions (pieces Zmm 2 )
- BN is the number of large protrusions (pieces / mm 2 )
- CN is the number of minute protrusions (pieces Zmm 2 ).
- the minute surface roughness RaS of the continuous thin film portion made solely of the resin forming the primer layer is 1.10 nm or less, and the surface roughness Ra of the continuous thin film is 1 to 1 O nm
- a polyester film for a magnetic recording medium is disclosed.
- a primer layer for a magnetic layer composed of a continuous thin film is coated on one surface of a polyester film, and the surface of the continuous thin film of the primer layer is (A) Small protrusions with a height of 13 nm or less with particles having an average particle diameter of less than 0.06 m and (B) Large protrusions with a height of 30 nm or less with particles having a particle diameter of 0.06 or more and ( C) Fine protrusions having a maximum major axis of 0.30 ⁇ or less are formed only by the resin that forms the primer layer.
- AN is the number of small protrusions (piece Zmm 2 )
- BN is the number of large protrusions (piece Zmm 2 )
- CN is the number of minute protrusions (piece Zmm 2 ).
- the minute surface roughness Ra S of the continuous thin film portion made solely of the resin forming the primer layer is 1.1 O nm or less, and the surface roughness Ra of the continuous thin film is 1 to 1 O nm, and the continuous thin film suppresses the precipitation rate of polyester oligomer monocrystals on the film surface to 0.8% or less when the film is continuously heated in air at 160 ° C. for 5 minutes.
- a possible polyester film for a magnetic recording medium is disclosed. According to the above polyester film, although the base film on the magnetic layer side can be smoothed to some extent, the dispersibility of the particles contained in the base film on the magnetic layer side is improved to improve running durability. Insufficiently, there were many oversized projections, which caused problems such as dropouts and uneven output of the magnetic head, resulting in lower output.
- the catalyst especially the antimony compound, added during the production of the polyester precipitates in the polyester.
- an antimony compound has a high polymerization rate, and has an advantage that the obtained polyester has excellent properties such as thermal stability, terminal lipoxyl group content, and softening point, but precipitates are generated in the polyester as described above. It has the disadvantage that.
- polyester polymerization catalyst examples include, in addition to the above-mentioned antimony compounds, for example, JP-B-47-15703, JP-B-47-16993, JP-B-47-147 JP-A-56-96 and the like disclose the use of germanium compounds, and JP-A-48-31293 and JP-A-52-33996 disclose the use of titanium compounds.
- a germanium compound when used, a precipitate such as an antimony compound is not generated, but the side reaction during the polymerization reaction is increased, so that the obtained polyester has a low softening point, and when a film is formed. Has the disadvantage that the mechanical strength of the film decreases.
- the polymerization rate is extremely high, and a precipitate such as an antimony compound is not formed, but there is a disadvantage that the heat stability of the obtained polyester is deteriorated.
- phosphorus compounds react with most polymerization catalysts, reducing the activity of the catalyst and generating precipitates.
- a titanium compound has a large degree of deactivation by a phosphorus compound.
- the heat setting temperature at the time of film formation is set to a normal temperature (205 to 2200). It is often necessary to set it higher (at 230 ° C). At that time, if the film stops running in the heat fixing device (stainless steel) due to film breakage, etc., the thin polyester film will undergo dry heat treatment at high temperature, and will surprisingly deteriorate in a short time.
- Japanese Patent Application Laid-Open No. 6-34734 discloses that a calcium compound, a magnesium compound, a phosphorus compound, and an antimony compound are used as a catalyst and a stabilizer, and the content and ratio thereof are specified. It is disclosed that by setting the content within the range, a polyester having excellent surface flatness in a film can be produced.
- Japanese Patent Application Laid-Open No. 7-48439 discloses that a calcium compound, a magnesium compound, a phosphorus compound, and a titanium compound are used as a catalyst and a stabilizer, and the content and ratio thereof are specified.
- JP-A-8-188704 discloses that a titanium compound, a germanium compound, an antimony compound, and a phosphorus compound are used as a catalyst and a stabilizer, and the content and ratio thereof are specified. Disclose a polyester composition having excellent dry heat deterioration property and antimony precipitation suppression property in a film.
- a first object of the present invention is to provide a biaxially oriented laminated polyester film which is excellent as a base film of a high-density magnetic recording medium having excellent running durability and electromagnetic conversion characteristics and having very little dropout.
- a second object of the present invention is to provide a biaxially oriented polyester film useful as a base film for a high-density magnetic recording medium which is excellent in dry heat deterioration property and precipitation foreign matter suppression property.
- the object of the present invention is to provide a laminated film comprising a base layer (A) formed of a polyester resin and a coating layer (B) formed on one surface thereof.
- the base layer (A) and the coating layer (B) are the following (1)
- the base layer (A) contains substantially no added fine particles or contains 0.001 to 0.1% by weight of added fine particles having an average particle size of 0.005 to 0.3 m
- the binder layer (B) contains a binder resin, added fine particles and a surfactant, and the added fine particles have an average particle diameter of 10 to 50 nm and a content of 0.5 to 30% by weight.
- (B) has a thickness of 3 to 40 nm
- the center plane average roughness (SRa) of the surface is 5 nm or less
- a biaxially oriented laminated polyester film for a magnetic recording medium comprising:
- the polyester resin forming the base layer (A) is an aromatic polyester resin generally known as a base film.
- the main acid component is terephthalic acid or naphthalenedicarboxylic acid. It is an acid, and it is a linear polyester having a film-forming ability and consisting mainly of ethylene glycol.
- This polyester may be a homopolyester or a copolyester.
- the polyester it is particularly preferred that at least 80 mol%, preferably at least 90 mol%, of all the repeating units are ethylene terephthalate units or ethylene-1,6-naphthalate units.
- the copolymerization components include diethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, polyethylene glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, etc.
- Other diol components other dicarponic acid components such as adipic acid, sebacic acid, fluoric acid, isofluoric acid, 5-sodium sulfoisophthalic acid, and oxycarboxylic acid components such as p-hydroxyxetoxybenzoic acid.
- the amount of these copolymer components is preferably at most 20 mol%, more preferably at most 10 mol%, based on the total acid components.
- a trifunctional or higher polyfunctional compound such as trimellitic acid or pyromellitic acid can be copolymerized.
- the amount is preferably such that the polymer is substantially linear, for example, 2 mol% or less.
- the polyester resin forming the base layer (A) may be a resin substantially free of added fine particles.
- added fine particles means fine particles that are intentionally added during the production of the polyester resin or the polyester resin.
- substantially not contained means that 0.001 It means that fine particles of not less than% by weight are not contained. Therefore, particles generated due to the catalyst or the stabilizer in the production of the polyester resin are not included in the category of the added fine particles.
- the polyester resin forming the base layer (A) preferably contains substantially no added fine particles, but contains fine particles of a specific size in a certain ratio depending on the purpose. be able to.
- the added fine particles When the added fine particles are contained in the polyester resin of the base layer (A), the added fine particles have an average particle diameter of 0.005 to 0.3 m, preferably 0.01 to 0.2 m, and particularly preferably 0.1 to 0.2 m. 02 to 0.2 wm, and its content is 0.001 to 0.1% by weight, preferably 0.005 to 0.08% by weight.
- the fine particles are contained in the polyester of the base layer (A)
- the running durability of the laminated polyester is improved. If the average particle diameter of the added fine particles exceeds 0.3 m, the electromagnetic conversion characteristics deteriorate, which is not desirable.
- the fine particles contained in the polyester resin of the base layer (A) have a volume shape coefficient (f) of 0.1 to ⁇ 6, more preferably 0.4 to ⁇ 6.
- the volume shape factor (f) is defined by the following equation.
- V is the volume of the particle (m 3 ), and R is the average particle size of the particle (/ m).
- the shape whose coefficient (f) is ⁇ 6 is a sphere (true sphere).
- the shape with a coefficient (f) of 0.4 to ⁇ 6 substantially includes an elliptical sphere such as a sphere (true sphere) and an oval shape.
- a volume shape factor (f) of less than 0.1 for example, it is difficult to obtain sufficient running durability with flaky particles.
- the relative standard deviation of the particle diameter of the fine particles represented by the following formula is preferably 0.5 or less, more preferably 0.3 or less, and particularly preferably 0.12 or less. If the relative standard deviation is larger than 0.5, the uniformity of projections when formed into a film becomes insufficient, which is not preferable. n
- a coating layer (B) is formed on one surface of the base layer (A).
- This layer (B) contains a binder resin, added fine particles and a surfactant, and has a thickness of 3 to 40 nm, preferably 4 to 30 nm.
- the added calo fine particles in the ⁇ layer (B) have an average particle size of 10 to 50 nm, preferably 15 to 45 nm, particularly preferably 18 to 40 nm, and the content thereof is 0.5 to 30% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight, based on the solid content (total amount of binder resin and surfactant) of the layer (B). % Range.
- binder resin in the layer (B) examples include a 7K polyester resin, an aqueous acryl resin and an aqueous polyester resin, and an aqueous polyester resin is particularly preferred. Next, the aqueous polyester resin will be specifically described.
- aqueous polyester resin examples include an acid component containing isophthalic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthylenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and adipic acid.
- Sebacic acid Sebacic acid, dodecanedicarboxylic acid, succinic acid, 5-Na sulfoisophthalic acid, 2-K sulfoterephthalic acid
- It is composed of one or more polyvalent carboxylic acids such as trimellitic acid, trimesic acid, trimellitic acid monopotassium salt, p-hydroxybenzoic acid and the like
- the daricol component is, for example, ethylene glycol, diethylene glycol, propylene glycol, 1 Of polyhydric hydroxy compounds such as 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, P-xylylene diol, dimethylolpropane, and ethylene oxide adduct of bisphenol A
- a polyester resin mainly composed of at least one kind is preferably used.
- a graft polymer or a block copolymer in which an acrylic polymer chain is bonded to a polyester chain, or an acryl-modified polyester resin in which two polymers form a specific physical configuration (IPN, core-shell) in a microscopic molecule Used similarly.
- aqueous polyester resin a type that dissolves, emulsifies, or finely disperses in water can be used freely, but a type that emulsifies or finely disperses in water is preferable.
- a sulfonic acid group, a carboxylic acid group, a polyether unit or the like may be introduced into the molecule.
- the type of the added fine particles in the coating film layer (B) is not particularly limited as long as it has the average particle size, but those having a relatively low specific gravity, which hardly settle in a coating liquid for forming a coating film, are preferred.
- heat-resistant polymers eg, cross-linked silicone resin, cross-linked acrylic resin, cross-linked polystyrene, melamine-formaldehyde resin, aromatic polyamide resin, polyamide-imide resin, cross-linked polyester, wholly aromatic polyester, etc.
- Particles, silicon dioxide (Silica), calcium carbonate and the like are preferred.
- crosslinked silicone resin particles, silica, and core-shell type organic particles for example, core: crosslinked polystyrene, shell: polymethyl methacrylate particles, etc.
- a nonionic surfactant is preferable, and in particular, a surfactant obtained by adding (poly) ethylene oxide to an alkyl alcohol, an alkylphenyl alcohol, a higher fatty acid, or the like is preferable.
- surfactants include, as polyoxetylene alkylphenyl ether-based compounds, trade names “Nonion NS—230” and “Non “S-240”, “HS-220”, “HS-240”, product names manufactured by Sanyo Chemical Co., Ltd. "Nonipol 200", “Nonipol 400”, “Nonipol 5""00”,”Ok Yun Paul 400”; trade names “Nonion E-230", “K-220”, and “Nonionic E-230” as polyoxyethylene alkyl ether compounds manufactured by NOF Corporation. Same as K-230 "; Examples of polyoxyethylene ester-based compounds of higher fatty acids such as” Nonion S-15.4 “and” S-40 "by Nippon Yushi Co., Ltd. Can be.
- the surfactant is preferably used in an amount of 10 to 50% by weight, more preferably 12 to 40% by weight, particularly preferably 15 to 30% by weight, based on the solid content of the coating layer (B). Used.
- the amount of the surfactant is less than 10% by weight (based on the total solid content), the generation of coarse projections that may cause dropout cannot be suppressed.
- the surfactant preferably has a softening point (measured by drying the surfactant) of 3 or more, measured in accordance with JISK 720, in order to improve the blocking resistance.
- a surfactant other than the above is added at 10% by weight (total solids). (Per minute) may be used in combination.
- the coating layer (B) has the composition and thickness described above, and its surface (the surface not in contact with the base layer (A)) has the following properties: ) To (d) It is necessary to satisfy the characteristics.
- Number of protrusions measured by enlarged surface photograph 3 5, 0 0 0 fold with a scanning electron microscope is from 1 to 4 0 Z m 2, preferably 2-2 0 ⁇ ⁇ 2 It is.
- the number of oversized projections having a major axis of 1 or more is 20 or less and Z cm 2 or less. Or 10 Z cm 2 or less.
- the center-surface average roughness (SRa) of the surface is 5 nm or less.
- the characteristic (a) is mainly due to the influence of projections on the surface of the base layer (A) caused by the added fine particles contained in the polyester resin of the base layer (A)
- the characteristic (c) is
- the base layer (A) mainly originated from large particles (particles resulting from precipitation of catalysts and stabilizers and particles mixed in from other sources) in the polyester tree J3 of the base layer (A). This is due to the effect of surface protrusions.
- the surface of the coating film layer (B) was measured with a scanning electron microscope at a magnification of 5,000 times, and the number of protrusions with a major axis of 0.05 or more was 80,000.
- 0 0 is 0 or Z mm 2 or less, preferably 6 0, 0 0 0 ZMM 2 below. Particularly preferably, the number is 500,000 Zmm 2 or less. This number mainly depends on the added fine particles contained in the polyester resin of the base layer (A). As described above, when the polyester resin of the base layer (A) does not contain added calo fine particles, the number of protrusions is extremely small.
- the lower limit of the number of the protrusions is 100,000 111111 2
- the preferable lower limit is 20,000 Zmm 2 .
- the number of the aforementioned protrusion is greater than 8 0, 0 0 0 Zm m 2, not desirable since the electromagnetic conversion characteristics deteriorated.
- the number of protrusions measured from a surface photograph of the coating layer (B) by a scanning electron microscope at a magnification of 35,000 times was 1 to 40 m2, and preferably 2 to 20 m2.
- Pieces // zm 2 The number of protrusions is more preferably 2.5 to 18 / m 2, and particularly preferably 3 to 15 Z m 2 .
- the projections in this surface characteristic (b) are mainly formed based on the added fine particles contained in the coating layer (B). Therefore, the number of the protrusions can be set in the above range by controlling the amount of the added fine particles contained in the coating layer (B).
- the surface property (c) of mmm (B) indicates the number of oversized protrusions.
- These oversized protrusions are protrusions having a major axis of 10 / xm or more, and the number should be 20 or less Zcm2.
- the size of the oversized protrusions is preferably 10 O / nm 2 or less.
- the protrusions having a height of 10 O nm or more have a high possibility of dropout and be as small as possible.
- the height of the projections is 1 0 O nm or more protrusions 1 0 Bruno cm 2 or less, it should be more favorable Mashiku the five cm 2 or less.
- the oversized projections in the surface characteristics (c) are mainly generated based on various large particles contained in the base layer (A) as described above.
- the oversized projections are mainly caused by dust mixed from the outside during film formation, or catalyst residue particles or poorly dispersed added fine particles that precipitate during polymerization of the polymer, but are particularly caused by catalyst residual particles or poorly dispersed added fine particles.
- the density of these oversized protrusions exceeds 20 cm 2 , it will cause dropout itself, and if it is caused by poor dispersion of the added fine particles, it will easily cause uneven wear of the head, and the electromagnetic conversion characteristics It is not preferable because it also worsens.
- a method of increasing the dispersibility of the added fine particles in the polyester resin for example, filtering the added slurry of the glycol slurry in advance with a fine filter to eliminate large particles including agglomeration.
- a method of optimizing the timing of feeding the polyester slurry as a glycol slurry a method of optimizing the feeding speed of the glycol slurry, or extruding a molten polymer from an extrusion die during film formation. It is preferable to carry out high-precision filtration before performing.
- the average opening of the filter is 50 to 400 times, more preferably 80 to 300 times the average particle diameter of the added fine particles.
- the lower limit of the average aperture is preferably set to 1 m.
- Another means of reducing the amount of oversized projections is to prevent them from forming oversized particles based on a catalyst or a stabilizer in the production of polyester. To do so, it is necessary to select the type and amount of the catalyst used and to control the ratio of the stabilizer. The use of these catalysts and stabilizers will be described later in detail.
- m (B) is the surface property (as the surface center plane average roughness (SR a)
- the force should be 5 nm or less, preferably 4 nm or less. If the surface roughness (SRa) exceeds 5 nm, the electromagnetic conversion characteristics deteriorate, which is not desirable.
- a thin film layer (C) may be further laminated on the surface of the base layer (A) which is not in contact with the coating layer (B).
- the laminate film (B) has a three-layer structure of the base layer (A) and the Z thin film layer (C), and the laminated film having this structure is a preferred embodiment of the present invention.
- This thin film layer (C) may be a layer formed by coating so as to be laminated on the surface of the base layer (A), or a film formed by co-extrusion when forming the film of the base layer (A). It may be. The latter is more preferred.
- the thin film layer (C) contains added fine particles. These added fine particles are referred to as “added fine particles C” to distinguish them from the added fine particles in the base layer (A) and the coating layer (B).
- the layer can be composed of a binder resin and added fine particles C, and can further contain a surfactant.
- the binder resin the added fine particles C and the surfactant, those similar to the binder resin, the added fine particles and the surfactant described for the layer (B) can be used.
- the added fine particles C preferably have an average particle diameter of 0.01 to 0.01 lm, more preferably 0.02 to 0.08 m, and particularly preferably 0.02 to 0.06 m.
- the thing is used.
- the amount of the added fine particles C is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight, and particularly preferably 2 to 10% by weight.
- the surfactant the surfactant can be used alone or in combination. Therefore, the composition of the thin film layer (C) can be the same as that of the layer (B).
- the thin film layer (C) may be formed of a polyester resin layer containing the added fine particles C, and may be formed by co-extrusion with the base layer (A).
- the thickness of the thin film layer (C), the average particle diameter of the added fine particles C, and the content thereof are as follows. It is desirable to satisfy the relational expression.
- d indicates the average particle size (um) of the added fine particles in the thin film layer (C)
- c indicates the content (% by weight) of the added fine particles
- t indicates the thickness of the thin film layer (C)
- the thin film layer (C) is a co-extruded layer with the base layer (A), it is advantageous to satisfy the following relational expression.
- the thin film layer (C) formed by co-extrusion contains the added fine particles C.
- the added fine particles C have the following average particle size and are contained in the following amounts.
- the average particle size (d) of the added fine particles C is preferably 0.1 to: Lm, more preferably 0.15 to 0.8 m, and particularly preferably 0.2 to 0.7 m.
- the content of the added fine particles C having the average particle diameter (d) is 0.001 to 1% by weight, more preferably 0.001 to 1% by weight based on the polyester resin or the binder resin of the thin film layer (C). It is preferably from 0.5 to 0.5% by weight, particularly preferably from 0.005 to 0.1% by weight.
- Examples of the added fine particles C include: (1) heat-resistant polymer particles (eg, cross-linked silicone resin, cross-linked polystyrene, cross-linked acrylic resin, melamine-formaldehyde resin, aromatic polyamide resin, polyimide resin, polyamide-imide resin, cross-linked (2) metal oxides (eg, aluminum trioxide, titanium dioxide, silicon dioxide, magnesium oxide, zinc oxide, zirconia oxide), (3) metal carbonates (eg, carbonic acid) (4) metal sulfates (eg, calcium sulfate, barium sulfate, etc.), (5) carbon (eg, carbon black, graphite, diamond, etc.), and (6) clay Minerals (eg, kaolin, clay, bentonite, etc.) are preferred.
- heat-resistant polymer particles eg, cross-linked silicone resin, cross-linked polystyrene, cross-linked acrylic resin, melamine-formaldehyde resin, aromatic polyamide resin, polyimide resin, polyamide-imide
- crosslinked silicone resin particles crosslinked polystyrene particles, melamine monoformaldehyde resin particles, polyamideimide resin particles, aluminum trioxide (alumina), titanium dioxide, silicon dioxide, zirconium oxide, Preference is given to synthetic calcium carbonate, barium sulfate, diamond and kaolin, especially preferred are crosslinked silicone resin particles, crosslinked polystyrene observation particles, alumina, titanium dioxide, silicon dioxide and calcium carbonate.
- the inert fine particles are composed of two or more kinds of particles
- the second and third particles having an average particle diameter smaller than the average particle diameter (d) of the additive fine particles C for example, colloidal silica, ⁇ , Fine particles such as alumina having a crystal form of ⁇ , ⁇ , 0, etc. can be preferably used in combination.
- fine particles having a small average particle diameter can be used among the particle types exemplified as the added fine particles C having the average particle diameter (d).
- the average particle size of the fine particles is in the range of 5 to 400 nm, more preferably 10 to 300 nm, particularly 30 to 250 nm, and is 50 nm or more, more preferably 100 nm or more than the average particle size (d). It is preferably smaller than 15 Onm.
- the content of the second and third particles (fine particles) is 0.005 to 1% by weight, more preferably 0.01 to 0.7% by weight, particularly 0.05 to 1% by weight of the resin of the thin film layer (C). It is preferably about 0.5% by weight.
- the thin film layer (C) has a thickness of 5 nm or more, preferably 8 nm or more, and the upper limit thereof is 12 or less, preferably 13 or less with respect to the total thickness of the laminated polyester film. Particularly preferred is a force S of 1Z4 or less.
- the biaxially oriented laminated polyester film according to the present invention has an air bleeding index (“air leak index” measured using a Beck smoothness tester, manufactured by Toyo Seiki Co., Ltd.) due to the presence of the thin film layer (C). It is preferred to show l to 2 KPaZhr.
- the biaxially oriented laminated polyester film of the present invention has the above-mentioned thin film layer (C) and exhibits an air bleeding index within the above range. The improvement of the retrievability is achieved.
- the air bleeding index when the thin film layer (C) is laminated by co-extrusion is 0.1 to 1.3 KPaZhr, preferably 0.3 to 1 KPaZhr.
- the laminated polyester film of the present invention when polyethylene terephthalate is used as the polyester resin in the base layer (A) or the thin film layer (C), those having an intrinsic viscosity in the range of 0.4 to 0.9 are used. Is done. This intrinsic viscosity is — Calculated from the viscosity measured as a solution in chlorophenol at a temperature of 35 ° C.
- the total thickness of the biaxially oriented laminated polyester film is usually 2.5 to 20 m, preferably 3.0 to 12 m, more preferably 4.0 to 12 mm.
- the biaxially oriented laminated polyester film of the present invention can be obtained according to a method known per se conventionally or accumulated in the art.
- the laminated structure of the base layer ( ⁇ ) and the thin film layer (C) is preferably produced by a co-extrusion method, and the lamination of the coating layer ( ⁇ ) is preferably carried out by a coating method.
- a base layer ( ⁇ ) and a thin film layer (C) are laminated by a co-extrusion method using a polyethylene terephthalate resin as a polyester resin is described in the extrusion die or before the die.
- the hold method, and the latter is called the feed block method).
- the above-mentioned polyethylene terephthalate resin ⁇ in which the added fine particles are finely dispersed and the polyethylene terephthalate resin C in which the added fine particles C are finely dispersed are further highly accurate.
- the unstretched laminated film is uniaxially (longitudinal or transverse) in a conventional manner in a temperature range of (Tg-10) to (Tg + 70) (where Tg is the glass transition temperature of the polyethylene terephthalate).
- the film is stretched at a magnification of 5 to 8.0 times, preferably at a magnification of 3.0 to 7.5 times. Further, if necessary, the film may be stretched again in the machine direction and the Z or transverse direction. That is, it is preferable to perform two-stage, three-stage, four-stage or multistage stretching.
- the total stretching ratio is usually 9 times or more, preferably 12 to 35 times, and more preferably 15 to 30 times, as the area stretching ratio.
- the biaxially oriented polyethylene terephthalate film is heat-set and crystallized at a temperature of (Tg + 70) to (Tm-10) ° C, for example, at 180 to 250, resulting in excellent dimensional stability. Is given.
- the heat setting time is 1 to 60 seconds. preferable.
- a coating liquid containing the above-mentioned added fine particles, a binder resin and a surfactant, preferably an aqueous coating liquid, is applied to the co-extruded polyester film to form a layer (B).
- the coating is preferably performed on the surface of the polyester layer (A) before the final stretching treatment, and after the coating, the film is preferably stretched in at least one direction. Before the stretching, it is dried on the way.
- the coating is preferably performed on an unstretched laminated film or a longitudinally (uniaxially) stretched laminated film, particularly a longitudinally (uniaxially) stretched laminated film.
- the application method is not particularly limited, and examples thereof include a roll coating method and a die coating method.
- the solid content of the above coating liquid, especially the aqueous coating liquid is preferably from 0.2 to 8% by weight, more preferably from 0.3 to 6% by weight, particularly preferably from 0.5 to 4% by weight.
- the coating liquid (preferably an aqueous coating liquid) contains other components such as other surfactants, stabilizers, dispersants, UV absorbers, and thickeners as long as the effects of the present invention are not impaired. Agents and the like can be added.
- an additive other than the above-mentioned added fine particles for example, a stabilizer, a coloring agent, a specific resistance modifier for the molten polymer, and the like can be added to the polyester resin, if desired.
- the Young's modulus of the laminated polyester film must be increased in the vertical and horizontal directions in order to improve various functions such as a head slider as a magnetic recording medium and running durability and at the same time to achieve a thinner film.
- the polyester is polyethylene terephthalate
- the degree of crystallinity is desirably 30 to 50%.
- the crystallinity is below the lower limit, the heat shrinkage increases, while if it exceeds the upper limit, the abrasion resistance of the film deteriorates, and white powder is liable to be generated when the film slides on the roll or guide pin surface.
- a preferred method for producing a polyester resin suitable for forming the base layer (A) of the present invention will be described.
- the surface characteristics of mm (B) on the surface of the base layer (A) require that the number of oversized projections be extremely small. Therefore, one of the causes of this oversized projection is the catalyst or stabilizer in the polyester resin. It is important to control the formation of large precipitate particles due to the above.
- the base layer (A) in the laminated polyester film of the present invention comprises: (a) at least one compound selected from the group consisting of an alkali metal compound, an alkaline earth metal compound and a manganese compound; b) A polyester resin containing at least one compound selected from the group consisting of a phosphorus compound and (c) a germanium compound, a titanium compound and an antimony compound in a proportion satisfying the following formulas (1) to (4) simultaneously. Desirably, it is a formed film.
- M is the total element of the alkali metal element, alkaline earth metal element and manganese element by compound (a), P is phosphorus element, Ti is titanium element, Ge is germanium element, and Sb is antimony. Indicates the amount (ppm) of the element in each polyester.
- the alkali metal element, the alkaline earth metal element, the manganese element, the phosphorus element, the titanium element, the antimony element and the germanium element are present in the polyester alone or as a compound. Therefore, it is necessary to optimize the contents and ratios of the alkali metal elements, alkaline earth metal elements, manganese element, phosphorus element, titanium element, antimony element and germanium element.
- a compound exhibiting an action capable of improving the reaction catalytic activity and stabilizing property at the time of producing a polyester or the electrostatic adhesion at the time of producing a film is preferable.
- oxides, chlorides, carbonates, potassium carbonates composed of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and norium are used.
- Acid salts and acetates are preferred, and lithium, sodium, potassium, cesium, magnesium, calcium, and barium acetates are particularly preferred.
- the manganese compound is preferably an oxide, a chloride, a carbonate, a carboxylate or the like, and particularly preferably an acetate.
- phosphoric acid ester such as phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, acidic methyl phosphate, phosphite, phosphite of trimethyl phosphite, methylphosphone Acid, phenylphosphonic acid, benzylphosphonic acid, phosphonic acid esters such as methylphosphonic acid methyl ester, phenylphosphonic acid ethyl ester, benzylphosphonic acid phenyl ester, etc., trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, etc. Preferred are mentioned.
- titanium compound examples include titanium tetrabutoxide, titanium trimellitate, tetraethoxytitanium, titanium sulfate, and titanium chloride.
- germanium compound examples include amorphous germanium dioxide, hexagonal gerilimanium dioxide, germanium chloride, and germanium phosphite.
- antimony compound examples include antimony trioxide, antimony pentoxide, antimony acetate, antimony potassium tartrate, antimony oxychloride, triphenylantimony and the like.
- these compounds are soluble in glycol.
- these compounds can be used alone or in combination of two or more.
- the total content (M) of the alkaline metal element, the alkaline earth metal element and the manganese element in the polyester must be in the range of 25 to 250 ppm, and is preferably It is within the range of 50 to 200 ppm (the above requirement 1). If this amount is less than 25 ppm, for example, in the production of polyester by the transesterification method, the transesterification reaction is delayed, which is not preferable, and even when the film is formed, the electrostatic adhesion is deteriorated and the productivity of the film is reduced. descend. On the other hand, if it exceeds 250 ppm, precipitated particles due to the compound of the contained element are generated, and the surface flatness is deteriorated when formed into a film.
- the ratio of the total content (M) of the alkali metal element, the alkaline earth metal element and the manganese element in the polyester (M) to the phosphorus element content (P) (MZ P) Needs to be in the range of 0.1 to 6.0, preferably in the range of 0.5 to 4.5, and more preferably in the range of 0.5 to 2.0. . If the ratio is less than 0.1 or exceeds 6.0, precipitated particles due to the compound of the contained element are generated, and the surface flatness is deteriorated when formed into a film.
- the polyester must contain a titanium compound, germanium compound or antimony compound as a polycondensation catalyst, and the content of titanium element must be 12.5 ppm or less, preferably 7 ppm or less. . If the amount is more than 12.5 ppm, the dry heat deterioration property during film formation deteriorates, which is not preferable.
- the content of the germanium element must be 110 ppm or less, and preferably 8 Oppm or less. If this amount exceeds 110 ppm, the dry heat resistance at the time of film formation is unfavorably deteriorated.
- the content of the antimony element needs to be 5 Oppm or less, and preferably 25 Oppm or less. If the amount is more than 50 ppm, black foreign matter due to antimony is likely to be generated, and in particular, in the case of polyethylene terephthalate, foreign matter increases over time due to film formation, which is not preferable. ⁇ 5).
- the titanium element and the germanium element among the above catalysts are preferably used in a total of 0.3 to 11 Oppm, preferably 1 to 80 ppm (the above-mentioned requirements).
- polyester there is no particular limitation on the timing and method of adding the alkali metal compound, alkaline earth metal compound, manganese compound, phosphorus compound, titanium compound, germanium compound, and antimony compound.
- an alkali metal compound, an alkaline earth metal compound, and a Z or manganese compound are preferably added until the intrinsic viscosity of the reactant reaches 0.2.
- the transesterification method it is preferable to add the compound before the start of the transesterification reaction because it can be used as a transesterification catalyst. At that time, the reaction may be carried out under normal pressure or under pressure, and it is particularly preferable to carry out the reaction under pressure, because the reaction time can be shortened.
- the order of addition may be such that each compound is added simultaneously or separately.
- the phosphorus compound is preferably added after the esterification reaction is substantially completed.
- it may be added all at once or in two or more portions.
- the titanium compound or the germanium compound is added at any time after the lapse of 10 minutes or more after the addition of the phosphorus compound and before the intrinsic viscosity reaches 0.3.
- the antimony compound may be added at any time before the intrinsic viscosity reaches 0.3.
- the polycondensation reaction time can be shortened by adding the phosphorus compound at the end of the polycondensation reaction.
- two or more polymers can be melt-blended using a rudder during film formation, and a master polymer containing a large amount of a phosphorus compound added is prepared and blended with a polymer using a titanium compound. It is also preferable to do so.
- soluble metal components may be contained in the polyester as long as the effects of the present invention are not impaired.
- a compound containing each element such as Zn and Co may be contained in the polyester.
- the number of oversized protrusions in the base layer (A) can be suppressed by using a combination of a catalyst and a stabilizer so as to satisfy requirements (1) to (4). Further, according to the study of the present inventor, it has been found that the number of oversized protrusions in the base layer (A) can be reduced by a combination other than the above-mentioned combination. That is, the base layer (A) in the laminated polyester film of the present invention is a film formed of a polyester resin containing a magnesium compound, a calcium compound, a titanium compound, and a phosphorus compound in proportions simultaneously satisfying the following formulas (1) to (4). Desirably.
- Mg, Ca, Ti and P represent the amounts (ppm) of the magnesium element, the calcium element, the titanium element and the phosphorus element in the respective polyesters.
- the calcium compound and the magnesium compound to be used oxides, chlorides, carbonates, carboxylates and the like are preferable, and particularly, acetates, that is, calcium acetate and magnesium acetate are preferable.
- the calcium compound and the magnesium compound may be added at any stage of the polyester production process.
- the calcium compound and the magnesium compound have, for example, an effect of lowering the specific resistance of the polyalkylene naphthalate at the time of melting.However, when a transesterification reaction between dimethyl naphthalenedicarboxylate and an aliphatic glycol is employed in the polymer production stage, Can also be used as a transesterification catalyst. Therefore, when it is also used as a transesterification catalyst, it must be added before the start of the transesterification reaction.
- the timing of addition of the calcium compound and the magnesium compound is not particularly limited, but it is possible to add these compounds until the intrinsic viscosity of the reaction product reaches 0.2. Since it is easy to uniformly disperse the particles, it can be exemplified as a preferable method.
- the order of addition may be such that both compounds are added at the same time or separately at different times.
- the esterification reaction can be performed without a catalyst.
- the addition amount of the calcium compound and the magnesium compound is, in the polyester,
- the total amount of the calcium element and the magnesium element is 25 to 200 ppm, preferably 50 to 180 ppm, and particularly preferably 70 to 16 ppm. ).
- a magnesium compound and a calcium compound soluble in this amount in the reaction system are added as a transesterification catalyst.
- this amount exceeds 200 ppm, the surface flatness is deteriorated when formed into a film due to the influence of the precipitated particles due to the catalyst, and it is not preferable. Not only is the transesterification reaction insufficient, but also the subsequent polymerization reaction is unfavorably slow.
- the ratio of ppm units of magnesium to calcium is 0.3 to 10, preferably 0.5 to 9, and particularly preferably 2.0 to 8.0 (KD required). If this ratio is less than 0.3, the surface flatness will be poor when formed into a film under the influence of the precipitated particles due to the catalyst. On the other hand, if it exceeds 10, various characteristics of the film are deteriorated, which is not preferable.
- the ratio of the total amount of calcium and magnesium to the phosphorus compound in units of ppm is 0.5 to 6.0, preferably 1.0 to 5.0, particularly preferably 2.0 to 5.0 ( Required mD). If the specific power in units of ppm exceeds 6, the surface flatness becomes worse when formed into a film due to the effect of precipitated particles due to the catalyst, while if it is less than 0.5, an excess amount of phosphorus compound relative to the transesterification catalyst is unfavorable. Therefore, the polycondensation reaction is delayed, which is not preferable.
- the same compounds as those described in the polyester can be exemplified.
- the phosphorus compound may be added before the polyester is formed into a film. For example, it may be added after the end of the esterification reaction or transesterification reaction or immediately before the polycondensation reaction. The addition may be carried out all at once or in two or more portions. It is also possible to add two or more polymers by melt-blending them with a ruder or the like during film formation. For example, a master-polymer containing a large amount of a phosphorus compound is prepared, and this is mixed with a titanium compound. It is also preferable to blend a polymer containing inert fine particles with a polymer (composition) that satisfies the above requirements (1) to (4). It is a good method.
- the titanium compound to be used is not particularly limited, but preferred examples thereof include titanium tetrabutoxide, titanium trimellitate, tetraethoxytitanium, titanium sulfate, and titanium chloride. Among them, titanium tetrabutoxide and titanium trimellitate are particularly preferable.
- such a titanium compound may be added before the start of the transesterification reaction, or may be added during the transesterification reaction, after the transesterification reaction is completed, and immediately before the polycondensation reaction.
- the esterification method it may be added after the esterification reaction is completed, or may be added immediately before the polycondensation reaction.
- the content of the titanium compound in the polyester as a titanium element is from 0.3 to 12.5 ppm, preferably from 1 to L ppm. If this amount exceeds 12.5 ppm, dry heat resistance due to the titanium compound tends to occur. On the other hand, if it is less than 0.3 ppm, the polymerization reaction is slow, which is not preferable.
- a magnetic recording medium having the aforementioned biaxially oriented laminated polyester film as a base film, that is, the biaxially oriented polyester film and the coating film layer (B) of the laminated film.
- a magnetic recording medium comprising a magnetic layer is similarly provided.
- Embodiments for manufacturing the magnetic recording medium of the present invention are as follows.
- the surface of the coating layer (B) of the biaxially oriented laminated polyester film may be coated with iron, copper, chromium, or an alloy or oxide containing these as main components by a method such as vacuum deposition, sputtering, or ion plating.
- a ferromagnetic metal thin film layer is formed, and a protective layer such as a diamond-like force (DLC) and a fluorinated carboxylic acid-based lubricating layer are sequentially provided on the surface of the ferromagnetic metal thin film layer according to purpose, application, and necessity.
- DLC diamond-like force
- fluorinated carboxylic acid-based lubricating layer are sequentially provided on the surface of the ferromagnetic metal thin film layer according to purpose, application, and necessity.
- the output in the short wavelength region, the electromagnetic conversion characteristics such as SZN, C / N, etc., especially dropout, error A low-rate, high-density recording vapor-deposited magnetic recording medium can be obtained.
- This vapor-deposited magnetic recording medium uses Hi 8 for analog signal recording, Digital Video Cassette Recorder (DVC) for digital signal recording, 8 mm data, It is extremely useful as a DSIV tape medium.
- DVC Digital Video Cassette Recorder
- iron or fine needle-like magnetic powder (metal powder) containing iron as a main component is made of polyvinyl chloride, vinyl chloride, or vinyl acetate. It is uniformly dispersed in a binder such as a copolymer, and applied so that the thickness of the magnetic layer is 1 m or less, preferably 0.1 to Lm.
- a metal-coated magnetic recording medium for high-density recording which has excellent output in the short wavelength region, excellent electromagnetic conversion characteristics such as SZN and CZN, and low dropout and error rate. can do.
- a nonmagnetic layer containing fine titanium oxide particles and the like may be formed on the base layer (A) as an underlayer of the metal powder-containing magnetic layer in the same organic binder as the magnetic layer. It can be dispersed and coated on the surface.
- This metal-coated magnetic recording medium supports 8 mm video for analog signal recording, Hi 8, / 3 cam SP, W-VHS, digital video cassette recorder (DVC) for digital signal recording, and 8 mm video recording. , DDSIV, Digital] 3 cam, D2, D3, SX, etc. It is extremely useful as a magnetic tape medium.
- a needle-like fine magnetic powder such as iron oxide or chromium oxide or a plate-like fine magnetic powder such as barium ferrite is coated with polyvinyl chloride.
- a coating such that the magnetic layer has a thickness of 1 m or less, preferably 0.1 to 1 lm, and if necessary, a thin film layer (C )
- it is particularly excellent in output in the short wavelength region, excellent in electromagnetic conversion characteristics such as SZN, CZN, etc., with low dropout and low error rate.
- An article-coated magnetic recording medium can be obtained.
- a nonmagnetic layer containing fine titanium oxide particles or the like may be dispersed on the thin film layer (C) as an underlayer of the magnetic layer in the same organic binder as the magnetic layer. , It can be painted.
- This magnetic recording medium coated with an oxide is useful as a magnetic recording medium coated with a high-density oxide such as QIC for data streamers for digital signal recording.
- VHS is a VTR for recording an analog HD TV signal.
- C is applicable for digital HD TV signal recording, and the biaxially oriented laminated polyester film of the present invention can be said to be a very useful base film for these HDTV-compatible VTR magnetic recordings.
- Average particle size I Average particle size: 0.06 m or more
- Particles having an average particle diameter of less than 0.06 m that form small protrusions are measured using a light scattering method. In other words, it is at the point of 50% by weight of all particles determined by the product name "NI COMP MODEL 270 SUBMI CRON PART I CLE SIZER” manufactured by Nikon Instrument Corporation. Expressed by the "equivalent spherical diameter" of the particle.
- the thickness of the entire film is randomly measured at 10 points with a micrometer and the average value is used.
- the thickness of layers A and C is determined by measuring the thickness of the thinner layer as described below, and the thickness of the thicker layer is calculated by subtracting the thickness of the thinner layer from the total thickness.
- Ask. In other words, using a secondary ion mass spectrometer (S IMS), the metal element (attributable to the highest concentration of particles in the film in the range of 5,000 nm in depth from the surface layer excluding the coating layer)
- the concentration ratio (M + ZC +) of the carbon element (C +) of the polyester (M +) and the polyester is defined as the particle concentration, and the analysis is performed in the thickness direction from the surface to a depth of 5, OO Onm.
- the particle concentration is low due to the interface of the surface, and the particle concentration increases as the distance from the surface increases.
- the particle concentration once increases to a stable value 2 after once reaching a stable value 1, and sometimes monotonously decreases.
- the depth gives the particle concentration of (stable value 1 + stable value 2) 2
- the particle concentration becomes 1 2 of the stable value 1 (This depth is deeper than the depth that gives a stable value of 1) is defined as the layer thickness of the layer.
- the measurement conditions are as follows.
- Particles most contained in the range of 5,000 nm from the surface layer are silicone resin
- FT-IR Fullier transform infrared spectroscopy
- XPS X-ray photoelectric spectroscopy
- the above is an effective measurement method for the co-extruded layer.
- the sample is observed with a transmission electron microscope (H-800 manufactured by Hitachi, Ltd.), and the layer thickness is determined from the layer boundary.
- Projection density of layer B surface by scanning electron microscope (measured at 5,000 times) The measurement of the projection density of the film surface is performed by scanning electron microscope.
- the measurement of the projection density on the film surface is performed by a scanning electron microscope. That is, 25 photographs of the surface of the coating layer (B) of the biaxially oriented polyester film were randomly taken at a magnification of 35,000 times, the frequency of surface protrusions was counted, and the number of protrusions per m 2 was calculated from the average value. Is converted to the projection density. Center plane average roughness SRa
- Z j k is the measurement direction (242 m) and the direction perpendicular to it (239 m)
- the surface of the coating layer (B) on which aluminum was deposited to a thickness of 0.5 m was magnified by differential interferometry using an optical microscope (NIKON CORP.), Trade name "OPT I PHOT". Observe the range of 1 cm x 5 cm at 200x, count the protrusions whose major axis is 1 Om or more, and convert to the number per 1 cm 2 to obtain the number of extra large protrusions. Number of oversized protrusions (projections with a height of 10 Onm or more)
- the front surface analysis by the roughness meter built software, up to the height protrusion height has a value precepts counts height 1 0 onm or more protrusions, oversized projections in terms of 1 cm 2 per number from baseline Number. Young's modulus Using a tensile tester manufactured by Toyo Paul Douin Co., Ltd.
- ⁇ is the Young's modulus ( ⁇ mm 2 )
- ⁇ is the stress difference due to the original average cross-sectional area between two points on the straight line
- ⁇ £ is the strain difference between the same two points.
- the film is hardly deteriorated and does not break even if it is pulled by hand.
- the film retains its shape, but it breaks when a strong bow is pulled by hand.
- the X film is in the form of a fine powder and is significantly inferior. Qualitative and quantitative analysis of metals in polyester
- the coating layer (B) of the biaxially oriented laminated film On the surface of the coating layer (B) of the biaxially oriented laminated film, two layers (each layer thickness of about 0.2 lm) of 100% cobalt ferromagnetic thin film is formed by vacuum evaporation to a thickness of 0.2 m. Then, a diamond-like carbon (DLC) film and a fluorine-containing carboxylic acid-based lubricating layer are sequentially provided on the surface, and a back coat layer is provided on the surface of the thermoplastic resin C side by a known method. Then slit into 8 mm width and load into a commercially available 8 mm video force set. Next, the characteristics of the tape are measured using the following commercially available equipment.
- DLC diamond-like carbon
- a signal with a recording wavelength of 0.5 m (frequency: about 7.4 MHz) was recorded, and the ratio of the reproduced signal, 6.4 MHz to 7.4 MHz, was used as the CZN of the tape, and the CZN of a commercially available 8 mm video evaporation tape was set to 0. Set to dB and judge with the following criteria.
- a 4.2 MHz video signal was recorded on the above-mentioned vapor-deposited tape, and a tape running speed of 4 lmZ and a rewinding speed of 41 mZ were run once under the conditions of a temperature of 25 ⁇ and a humidity of 50% RH.
- ⁇ The output fluctuation after 200 repetitions is ⁇ 0.3 dB to 0.6 dB.
- Acetic acid prepared by dissolving 100 parts of dimethyl terephthalate and ethylene glycol 7 ⁇ ⁇ 15 in ethylene glycol in advance and filtering with high precision through a 0.1 m filter (hereinafter abbreviated as “solution filtration”) Using a magnesium 4 ⁇ salt ethylene glycol solution (equivalent to 0.045 parts as magnesium acetate tetrahydrate) and a calcium acetate 17 salt ethylene dalicol solution (equivalent to 0.0035 parts as calcium acetate monohydrate), in a conventional manner After transesterification according to the above, a solution-filtered trimethylphosphoethylene dalicol solution (equivalent to 0.011 part as trimethylphosphoate) was added to substantially terminate the transesterification reaction.
- solution filtration Using a magnesium 4 ⁇ salt ethylene glycol solution (equivalent to 0.045 parts as magnesium acetate tetrahydrate) and a calcium acetate 17 salt ethylene dalicol solution (equivalent to 0.0035 parts as calcium acetate mono
- the polyethylene terephthalate tree A and resin C were each dried at 170 for 3 hours, fed to two extruders, and melted at a melting temperature of 280 to 300, with resin A having an average opening of 10 zm.
- Resin C is filtered with a steel wire filter with an average opening of 30 m using a steel wire filter with high precision. After that, using a multi-manifold coextrusion die, the resin layer (C) is applied to one side of the resin layer (A). ) And quenched to obtain an unstretched laminated film having a thickness of 89 m.
- the obtained unstretched film is pre-heated, stretched 3.3 times at a film temperature of 100 ° C between low-speed and high-speed rolls, quenched, and then Takamatsu is added to the layer (A) of the longitudinally stretched film.
- the thickness of (C) was adjusted so that the C layer had a thickness of 1.0 m by the discharge rates of the two extruders.
- the Young's modulus of this film is 500 kgZmm 2 (4, 9 0 N / mm 2 ) and 700 kg in the lateral direction mm 2 (6,86 O NZmm 2 ).
- Table 1 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat deterioration properties and surface characteristics of the biaxially oriented laminated film, and the characteristics of the ferromagnetic thin film deposited tape using this film.
- Example 2 After the transesterification reaction was terminated in the same manner as in Example 1, a solution-filtered ethylene glycol solution of titanium trimellitate (equivalent to 0.01 part by weight of titanium trimellitate) was added, and 0.1 m in advance was further added. An ethylene glycol slurry of spherical silica having an average particle diameter of 0.06 m filtered through an aperture filter 1 was added so that the concentration in the polyester was 0.05% by weight, and then the mixture was continuously heated at a high temperature and high vacuum. Polycondensation was carried out in the usual manner to obtain a polyethylene terephthalate resin A having an intrinsic viscosity of 0.60. Thereafter, a biaxially oriented laminated polyester film was obtained in the same manner as in Example 1. Young's modulus of the film is machine direction 5 0 0 k gZmm 2 (4 , 9 0 O NZmm 2), was laterally 7 0 0 k gZmm 2 (6 , 8 6 O NZmm 2).
- Table 1 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat deterioration property and surface properties of the biaxially oriented laminated film, and the properties of the ferromagnetic thin film deposited tape using this film.
- Example 3 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat deterioration property and surface properties of the biaxially oriented laminated film, and the properties of the ferromagnetic thin film deposited tape using this film.
- Calcium acetate 17jc salt ethylene dalichol solution (equivalent to 0.033 parts as calcium acetate monohydrate) and magnesium acetate obtained by filtering solution of 100 parts of dimethyl terephthalate and 70 parts of ethylene glycol as ester exchange catalysts After transesterification according to a conventional method using 4 ⁇ salt ethylene glycol solution (equivalent to 0.044 parts of magnesium acetate tetrahydrate), the solution was filtered, and the trimethyl phosphate ethylene glycol solution ( 0.012 parts) was added as trimethyl phosphate to substantially terminate the transesterification reaction.
- the solution is filtered After the addition of ethylene tetrabutoxide ethylene glycol solution (equivalent to 0.007 parts of titanium tetrabutoxide), polycondensation is carried out in a conventional manner under high temperature and high vacuum, and polyethylene terephthalate having an intrinsic viscosity of 0.60 is added. Got the rate.
- manganese acetate 47-salt ethylene dalicol solution (equivalent to 0.05 parts of manganese acetate tetrahydrate) obtained by solution filtration of 100 parts of dimethyl terephthalate and 70 parts of ethylene glycol as ester exchange catalysts 20 minutes after the start of methanol distillation, the solution was filtered (when dissolved in ethylene glycol, heat treatment was performed).
- Antimony trioxide ethylene glycol solution (0.024 parts as an antimony trioxide)
- transesterification according to a conventional method.
- a trimethyl phosphate ethylene glycol solution (equivalent to 0.135 parts as trimethyl phosphate) filtered through the solution was added, and the transesterification was substantially carried out.
- Polyethylene terephthalate resin A was obtained by mixing the polymer pellets obtained in 1 and 2 above at a weight ratio of about 8: 2 (ratio of 1 to)).
- a biaxially oriented laminated polyester film was obtained in the same manner as in Example 1, except for changing to.
- the Young's modulus of this film was 500 kg / mm 2 (4,900 N / mm 2 ) in the longitudinal direction and 700 kgZmm 2 (6,86 O / mm 2 ) in the transverse direction.
- Table 1 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat deterioration properties and surface characteristics of the biaxially oriented laminated film, and the characteristics of the ferromagnetic thin film deposited tape using this film.
- Example 4
- Example 3 Solution-filtered titanium tetrabutoxide of Example 3 A biaxially oriented laminated polyester film was obtained in the same manner as in Example 3, except that the ethylene glycol solution was changed to 0.014 parts as germanium dioxide. Young's modulus of the film is machine direction 500 kgZmm 2 (4, 90 ON / mm 2), was transverse 700 kg / mm 2 (6, 86 ON / mm 2).
- Table 1 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat deterioration properties and surface characteristics of the biaxially oriented laminated film, and the characteristics of the ferromagnetic thin film deposited tape using this film.
- Example 5 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat deterioration properties and surface characteristics of the biaxially oriented laminated film, and the characteristics of the ferromagnetic thin film deposited tape using this film.
- ethylene daricol solution (as calcium acetate monohydrate) obtained by solution filtration of 100 parts of dimethyl 2,6-naphthalate (dimethyl 2,6-naphthalene dicarboxylate) and 70 parts of ethylene glycol as a transesterification catalyst. 0.026 parts) and magnesium acetate 47-salt ethylene glycol solution (equivalent to 0.035 parts as magnesium acetate 4 ⁇ salt), followed by transesterification according to a conventional method, followed by filtration of the solution of trimethylphosphine. A polyethylene glycol solution (0.010 parts as trimethyl phosphate) was added to substantially terminate the transesterification reaction.
- Particles and spherical silica with an average particle size of 0.1 m are added so that the concentration in the polymer becomes 0.07 wt% and 0.2 wt%, respectively, and polyethylene with an intrinsic viscosity of 0.60—2,6-naphthalate Resin C was obtained.
- the polyethylene 1,2,6-naphtholate resin A and resin C were each dried at 170 ° C for 6 hours, then fed to two extruders, and melted at a melting temperature of 300 to 310 ° C.
- Resin C was filtered with a steel wire filter with an average opening of 13 m and high precision with a steel wire filter with an average opening of 30 respectively. Then, using a multi-manifold coextrusion die, the resin layer (A) The resin layer (C) was laminated on one side, and quenched to obtain an unstretched laminated film having a thickness of 117 am.
- the obtained unstretched film is preheated, further stretched 3.8 times at a film temperature of 130 ° C between low-speed and high-speed rolls, quenched, and then Takamatsu is placed on the layer (A) side of the longitudinally stretched film.
- Acryl-modified polyester manufactured by Yushi Co., Ltd. 65 parts of “IN-170-6” (57 ° C softening point) and 29 parts of “Nonion NS-240” (softening point of 46 ° C) manufactured by NOF Corporation 1 part of "Nonion NS-208.5” (softening point 10 ° C or less) manufactured by NOF Corporation, and 5 parts of an acrylic filter with an average particle diameter of 30 nm. 1.0% by weight) by the kiss coat method.
- the obtained biaxially stretched film was heat-set with hot air at 200 ° C. for 4 seconds to obtain a biaxially oriented laminated polyester film having a coating layer (B) thickness of 8 nm and a total film thickness of 6.4 m.
- the thicknesses of the layers (A) and (C) were adjusted so that the layer (C) became 1 by the discharge rates of the two extruders. Young's modulus of the film longitudinal direction 5, 00 ON / mm 2, was transverse 9, 00 ON / mm 2.
- Table 1 shows the content of the soluble metal component in this polyethylene 1,2,6-naphthalate resin A, the dry heat deterioration and surface characteristics of this biaxially oriented laminated film, and the characteristics of the ferromagnetic thin film deposited tape using this film. Show.
- Example 6
- polyethylene terephthalate resin A was carried out in the same manner as in Example 1. This resin A was dried at 170 ° C for 3 hours, fed to an extruder, melted at a melting temperature of 280 to 300 ° C, and averaged. After high-precision filtration using a steel wire filter with a mesh size of 10 m, it was rapidly cooled using a slit die to obtain an unstretched film having a thickness of 89 m.
- the obtained unstretched film is preheated, stretched 3.3 times at a film temperature of 100 ° C between low and high speed rolls, quenched, and then coated on one side of the vertically stretched film (B).
- a film temperature of 100 ° C between low and high speed rolls quenched, and then coated on one side of the vertically stretched film (B).
- composition containing 29 parts of “240” (with a softening point of 46), 1 part of “Nonion NS—2 08.5” (softening point of 10 or less) manufactured by NOF Corporation, and 5 parts of an acrylic filler with an average particle size of 3 Onm.
- the obtained biaxially stretched film was heat-set with hot air at 220 ° C for 4 seconds, and the thickness of the thin layer (B) was 8 nm, the thin film layer (C) (collectively formed) was 15 nm, and the total film thickness was 6.4 m.
- a biaxially oriented laminated polyester film was obtained.
- the Young's modulus of this film was 500 kg / mm 2 (4,900 NZmm 2 ) in the vertical direction and 700 kg / mm 2 (6,860 N / mm 2 ) in the horizontal direction.
- Table 1 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat deterioration properties and surface characteristics of the biaxially oriented laminated film, and the characteristics of the ferromagnetic thin film deposited tape using this film. Comparative Example 1
- Example 2 When preparing polyethylene terephthalate resin A, the procedure was the same as in Example 1, except that magnesium acetate 4 ⁇ salt used as the transesterification catalyst was changed to 0.065 parts and calcium acetate monohydrate to 0.060 parts. A biaxially oriented film was obtained. Young's modulus of the film is machine direction 500 k gZmm 2 (4, 90 ON / mm 2), was transverse 700 kgZmm 2 (6, 86 ON Roh mm 2).
- Table 1 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat deterioration properties and surface characteristics of the biaxially oriented laminated film, and the characteristics of the ferromagnetic thin film deposited tape using this film. Comparative Example 2
- biaxially oriented laminated polyethylene was used in the same manner as in Example 1 except that a steel wire filter with an average opening of 1 ⁇ was changed to a steel wire filter with an average opening of 20 m.
- a terephthalate film was obtained.
- the Young's modulus of this film longitudinal direction 500 kgZmm 2 (4, 900 N / mm 2), was transverse 700 kgZmm 2 (6, 860 NZmm 2).
- Table 1 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat deterioration property and surface properties of the biaxially oriented laminated film, and the properties of the ferromagnetic thin film tape using this film. Comparative Example 3
- polyethylene terephthalate resin A As a polyethylene terephthalate resin A, an ethylene glycol slurry of spherical silica having an average particle size of 0.26 / xm, which was previously filtered through a filter with a 0.5 m opening, had a concentration of 0.1 wt% in the polymer.
- a biaxially oriented laminated polyethylene terephthalate film was obtained in the same manner as in Example 2 except that the film was included as described above. Young's modulus of the full Ilm longitudinal direction 500 k gZmm 2 (4, 90 ON / mm 2), was transverse 700 kg / mm 2 (6, 86 ON / mm 2).
- Table 1 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat resistance and the surface characteristics of the biaxially oriented laminated film, and the characteristics of the ferromagnetic thin film deposited tape using this film. Comparative Example 4
- a biaxially oriented film was obtained in the same manner as in Example 1, except that when preparing polyethylene terephthalate resin A, the amount of titanium trimellitate used as the polycondensation catalyst was changed to 0.026 parts.
- the Young's modulus of this film was 500 kg / mm 2 (4,900 NZmm 2 ) in the vertical direction and 700 kgZmm 2 (6,86 ON / mm 2 ) in the horizontal direction.
- Table 1 shows the content of the soluble metal component in the polyethylene terephthalate resin A and the dry heat deterioration properties and surface properties of the biaxially oriented laminated film. Since this film was greatly deteriorated in the dry heat deterioration evaluation, the subsequent evaluation of the characteristics of the ferromagnetic thin film deposited tape was stopped. Comparative Example 5
- Table 1 shows the content of the soluble metal component in the polyethylene terephthalate resin A, the dry heat resistance and the surface characteristics of the biaxially oriented laminated film, and the characteristics of the ferromagnetic thin film deposited tape using this film.
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Example ⁇ Type of fine particles added with base A None Spherical filler None None None None Average particle size ( ⁇ ) 0.06
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Coating B Number of protrusions at 5,000 times (/ mm 2 ) 0 26000 0 0 0 0 0
- the biaxially oriented polyester films of the examples show excellent electromagnetic conversion characteristics, and have few extra-large projections that cause dropout, and are excellent.
- the comparative film cannot satisfy these characteristics at the same time.
Landscapes
- Laminated Bodies (AREA)
- Magnetic Record Carriers (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT99951191T ATE444552T1 (de) | 1998-11-02 | 1999-11-01 | Biaxial orientiertes polyesterfilm-laminat für magnetische aufzeichnungsmedien |
EP99951191A EP1047048B1 (en) | 1998-11-02 | 1999-11-01 | Biaxially oriented laminated polyester film for magnetic recording medium |
DE69941479T DE69941479D1 (de) | 1998-11-02 | 1999-11-01 | Biaxial orientiertes polyesterfilm-laminat für magnetische aufzeichnungsmedien |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10/311963 | 1998-11-02 | ||
JP31196498A JP2000149246A (ja) | 1998-11-02 | 1998-11-02 | 磁気記録媒体用積層ポリエステルフィルム |
JP31196398 | 1998-11-02 | ||
JP10/311964 | 1998-11-02 | ||
JP4418499 | 1999-02-23 | ||
JP11/44183 | 1999-02-23 | ||
JP4418399 | 1999-02-23 | ||
JP11/44184 | 1999-02-23 |
Publications (1)
Publication Number | Publication Date |
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WO2000026903A1 true WO2000026903A1 (fr) | 2000-05-11 |
Family
ID=27461497
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1999/006080 WO2000026903A1 (fr) | 1998-11-02 | 1999-11-01 | Film polyester stratifie a orientation biaxiale pour support d'enregistrement magnetique |
Country Status (8)
Country | Link |
---|---|
US (1) | US6670030B1 (ja) |
EP (1) | EP1047048B1 (ja) |
KR (1) | KR100437360B1 (ja) |
CN (1) | CN1161758C (ja) |
AT (1) | ATE444552T1 (ja) |
DE (1) | DE69941479D1 (ja) |
TW (1) | TW563105B (ja) |
WO (1) | WO2000026903A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000309649A (ja) * | 1999-02-23 | 2000-11-07 | Teijin Ltd | 2軸配向ポリエステルフィルム |
KR100855525B1 (ko) | 2001-02-23 | 2008-09-01 | 데이진 가부시키가이샤 | 적층 폴리에스테르 필름 및 자기기록매체 |
JP2010285527A (ja) * | 2009-06-11 | 2010-12-24 | Toyobo Co Ltd | フィルム用ポリエステル組成物およびその製造方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US7048994B2 (en) * | 2001-02-23 | 2006-05-23 | Teijin Limited | Laminated polyester film and magnetic recording medium |
DE10152141A1 (de) * | 2001-10-23 | 2003-04-30 | Mitsubishi Polyester Film Gmbh | Matte, biaxial orientiertge Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
US7344786B2 (en) * | 2001-10-29 | 2008-03-18 | Fujifilm Corporation | Magnetic recording medium including a smooth coating layer on one side of the support |
EP1502734B1 (en) * | 2002-05-02 | 2014-09-17 | Teijin Dupont Films Japan Limited | Laminated film for optical use |
TW200408531A (en) * | 2002-09-05 | 2004-06-01 | Teijin Dupont Films Japan Ltd | Base film for membrane switch and membrane switch |
KR100843397B1 (ko) * | 2002-10-03 | 2008-07-03 | 도레이 가부시끼가이샤 | 폴리에스테르 수지 조성물, 폴리에스테르 제조용 촉매,폴리에스테르 필름 및 자기기록매체 |
US7176274B1 (en) * | 2002-11-04 | 2007-02-13 | Saehan Industries Incorporated | Saturated polyester for plastic containers with excellent heat resistance and gas impermeability and method for manufacturing the same |
DE10301786A1 (de) * | 2003-01-20 | 2004-07-29 | Mitsubishi Polyester Film Gmbh | Mehrschichtige transparente, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10303145A1 (de) * | 2003-01-28 | 2004-07-29 | Mitsubishi Polyester Film Gmbh | Einseitig matte, biaxial orietierte Polyesterfolie mit charakteristischen Schrumpfeigenschaften, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10303144A1 (de) * | 2003-01-28 | 2004-07-29 | Mitsubishi Polyester Film Gmbh | Einseitig matte, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
JP2004265466A (ja) | 2003-02-07 | 2004-09-24 | Toray Ind Inc | 記録媒体用ポリエステルフィルム及び磁気記録テープ |
JP2005018821A (ja) * | 2003-06-23 | 2005-01-20 | Fuji Photo Film Co Ltd | 磁気記録媒体および磁気記録再生方法 |
WO2006025344A1 (ja) * | 2004-08-30 | 2006-03-09 | Mitsubishi Polyester Film Corporation | 離型用ポリエステルフィルム |
JP5915102B2 (ja) * | 2011-11-11 | 2016-05-11 | 東レ株式会社 | 二軸配向ポリエステルフィルムおよび磁気記録媒体 |
CN103630472B (zh) * | 2013-11-28 | 2015-12-30 | 南京大学 | 一种定量描述碳纳米管悬浮液聚集和沉降行为的方法 |
CN108035044A (zh) * | 2017-12-28 | 2018-05-15 | 宁波三同编织有限公司 | 一种有机硅-聚酰亚胺改性耐高温聚酯纤维面料及其制备方法 |
JP2021038388A (ja) * | 2019-09-02 | 2021-03-11 | 東洋紡フイルムソリューション株式会社 | 二軸配向ポリエステルフィルム |
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JP3258259B2 (ja) * | 1996-07-31 | 2002-02-18 | 帝人株式会社 | 積層フィルム |
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1999
- 1999-11-01 TW TW88118950A patent/TW563105B/zh not_active IP Right Cessation
- 1999-11-01 WO PCT/JP1999/006080 patent/WO2000026903A1/ja active IP Right Grant
- 1999-11-01 DE DE69941479T patent/DE69941479D1/de not_active Expired - Lifetime
- 1999-11-01 AT AT99951191T patent/ATE444552T1/de not_active IP Right Cessation
- 1999-11-01 KR KR10-2000-7007393A patent/KR100437360B1/ko not_active IP Right Cessation
- 1999-11-01 EP EP99951191A patent/EP1047048B1/en not_active Expired - Lifetime
- 1999-11-01 US US09/582,820 patent/US6670030B1/en not_active Expired - Lifetime
- 1999-11-01 CN CNB99803536XA patent/CN1161758C/zh not_active Expired - Fee Related
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JPH0748439A (ja) * | 1993-08-04 | 1995-02-21 | Teijin Ltd | ポリエステルの製造方法 |
JPH08188704A (ja) * | 1995-01-10 | 1996-07-23 | Teijin Ltd | ポリエステル組成物 |
EP0822220A2 (en) * | 1996-07-31 | 1998-02-04 | Teijin Limited | Laminate film |
Cited By (3)
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JP2000309649A (ja) * | 1999-02-23 | 2000-11-07 | Teijin Ltd | 2軸配向ポリエステルフィルム |
KR100855525B1 (ko) | 2001-02-23 | 2008-09-01 | 데이진 가부시키가이샤 | 적층 폴리에스테르 필름 및 자기기록매체 |
JP2010285527A (ja) * | 2009-06-11 | 2010-12-24 | Toyobo Co Ltd | フィルム用ポリエステル組成物およびその製造方法 |
Also Published As
Publication number | Publication date |
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TW563105B (en) | 2003-11-21 |
ATE444552T1 (de) | 2009-10-15 |
KR100437360B1 (ko) | 2004-06-25 |
EP1047048B1 (en) | 2009-09-30 |
US6670030B1 (en) | 2003-12-30 |
CN1161758C (zh) | 2004-08-11 |
KR20010033835A (ko) | 2001-04-25 |
CN1292135A (zh) | 2001-04-18 |
EP1047048A1 (en) | 2000-10-25 |
EP1047048A4 (en) | 2000-12-20 |
DE69941479D1 (de) | 2009-11-12 |
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