WO2015019885A1 - Laminated polyester film - Google Patents
Laminated polyester film Download PDFInfo
- Publication number
- WO2015019885A1 WO2015019885A1 PCT/JP2014/069817 JP2014069817W WO2015019885A1 WO 2015019885 A1 WO2015019885 A1 WO 2015019885A1 JP 2014069817 W JP2014069817 W JP 2014069817W WO 2015019885 A1 WO2015019885 A1 WO 2015019885A1
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- WIPO (PCT)
- Prior art keywords
- layer
- film
- polyester film
- laminated polyester
- resin constituting
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/027—Thermal properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/24—Organic non-macromolecular coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02K—DYNAMO-ELECTRIC MACHINES
- H02K3/00—Details of windings
- H02K3/30—Windings characterised by the insulating material
Definitions
- the present invention relates to a laminated polyester film having good heat resistance and wet heat resistance and excellent workability.
- Polyester resins especially polyethylene terephthalate (hereinafter sometimes abbreviated as PET) and polyethylene 2,6-naphthalene dicarboxylate (hereinafter sometimes abbreviated as PEN) are mechanical properties, thermal properties, chemical resistance, electrical properties, It has excellent moldability and is used for various purposes.
- Polyester films made from polyester, especially biaxially oriented polyester films, are used in solar cell backsheets, water heater motor electrical insulation materials, and hybrid vehicles because of their excellent mechanical and electrical properties. It is used as various industrial materials such as electric insulation materials, magnetic recording materials, capacitor materials, packaging materials, building materials, photographic applications, graphic applications, thermal transfer applications, etc.
- PEN when used for electrical insulating materials (for example, compressor motors for air conditioners), it is used in an environment where the temperature becomes high as the refrigerant is compressed and expanded.
- PEN was often used (Patent Documents 1 and 2).
- PEN has poor processability due to its molecular structure, and causes a problem that the film breaks during processing. Therefore, a special processing step is required to solve such a problem (Patent Document 3).
- so-called wet heat resistance that does not cause degradation due to hydrolysis even under high-temperature and high-humidity conditions is required to withstand long-term use.
- HFC hydrofluorocarbon
- HCFC hydrochlorofluorocarbon
- the object of the present invention is to provide a film excellent in heat resistance, moist heat resistance and processability in view of the background of such conventional technology.
- the present invention has the following configuration. That is, [I] A laminated polyester film comprising at least two layers that satisfies the following requirements (1) to (3). (1) at least one surface, when measured by Fourier transform infrared spectroscopy (FT-IR), and the spectral intensity r1 observed in 1452Cm -1, the spectrum intensity r2 observed in 1332 cm -1 R1 and R2 obtained from the spectral intensity r observed at 1602 cm ⁇ 1 satisfy the following relationship.
- FT-IR Fourier transform infrared spectroscopy
- the layer B is obtained from a spectral intensity r4 observed at 1388 cm ⁇ 1 and a spectral intensity r5 observed at 1372 cm ⁇ 1 when measured by Fourier transform infrared spectroscopy (FT-IR).
- FT-IR Fourier transform infrared spectroscopy
- R4 r4 / r5
- the laminated polyester film according to any one of [I] to [IV] in which both surface layers of the film are composed of A layers and are composed of at least three layers.
- the present invention it is possible to provide a polyester film that is excellent in heat resistance, heat and humidity resistance, and processability and that satisfies long-term use. Since the film obtained by the present invention suppresses deterioration of physical properties even under high temperature and high humidity conditions, a laminated polyester film that can withstand long-term use even when used as an electric insulating member of a motor using a refrigerant composed of HFC Can be provided.
- the polyester film of the present invention needs to be a laminated polyester film composed of at least two layers.
- Polyester here is a polymer having an ester bond synthesized from a dicarboxylic acid component and a diol component as the main bond chain.
- a structural component shows the minimum unit which can be obtained by hydrolyzing polyester.
- dicarboxylic acid component constituting the polyester examples include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalon.
- Aliphatic dicarboxylic acids such as acid, ethylmalonic acid and the like, adamantane dicarboxylic acid, norbornene dicarboxylic acid, cyclohexanedicarboxylic acid, decalin dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene Dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 5-sodium sulfoisophthalate Acid, fu Examples thereof include, but are not limited to, dicarboxylic acids such as nylendanedicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, aromatic dicarbox
- diol component constituting the polyester examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol.
- Aliphatic diols such as cyclohexanedimethanol and spiroglycol, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9′-bis (4-hydroxy Examples include, but are not limited to, diols such as aromatic diols such as phenyl) fluorene, and a series of a plurality of the aforementioned diols.
- the laminated polyester film of the present invention must satisfy the following (1).
- Ii 1.25 ⁇ R2 ⁇ 1.50
- R1 r1 / r
- R2 r2 / r.
- polyethylene 2,6-naphthalenedicarboxylate is contained in the resin constituting the layer having a surface satisfying (1).
- the content of polyethylene 2,6-naphthalenedicarboxylate in the resin constituting the layer having the surface satisfying (1) constitutes the layer having the surface satisfying (1) from the viewpoint of heat resistance and heat and moist heat resistance. It is preferable that it exceeds 70 mass% with respect to the total amount of resin, More preferably, it is 85 mass% or more.
- polyethylene 2,6-naphthalenedicarboxylate is known to have two types of conformation of the methylene group of polyethylene 2,6-naphthalate: a Gauche structure and a trans structure.
- the trans structure is advantageous over the Gauche structure when the molecular chains are regularly arranged. Therefore, the Gauche type structure reflects the part where the molecular chain of polyethylene 2,6-naphthalene dicarboxylate is not regularly arranged (hereinafter referred to as amorphous part), and the trans type structure is polyethylene 2,6-naphthalene dicarboxylate.
- the molecular chains of the rate are oriented and regularly arranged to reflect a crystallized structure (hereinafter referred to as a crystal portion).
- the conformation Gauche structure of the methylene group of polyethylene 2,6-naphthalate was observed at 1452 cm ⁇ 1 .
- the trans-type structure is characterized by the spectrum observed at 1332 cm ⁇ 1 . That is, r1 reflects a Gauche structure derived from the amorphous part, and r2 reflects a trans structure derived from the crystalline part.
- the spectral intensity r observed at 1602 cm ⁇ 1 reflects absorption due to C—H stretching vibration of the naphthalene ring of polyethylene 2,6-naphthalene dicarboxylate and does not depend on the arrangement of molecular chains. It can be used as a standardized absorption peak in intensity comparison. Therefore, the smaller R1 which is r1 / r and the larger R2 which is r2 / r, the more crystal parts having a regular structure.
- the heat resistance and heat-and-moisture resistance increase as the number of crystal parts increases.
- the mechanical strength of the film is derived from a crystal part in which molecular chains are regularly arranged.
- the mechanical elongation is derived from an amorphous part, not only heat resistance and moist heat resistance but also workability is improved. Therefore, it is important that the crystal part and the amorphous part are in a certain range, that is, R1 and R2 are in a range satisfying the expressions (i) and (ii).
- the polyester resin constituting the surface satisfying (1) is a polyester resin that satisfies the following condition (iii), and the film is biaxially oriented under the conditions described later. Can be obtained.
- the orientation of the film is related to the mobility of the polyester molecular chain. As will be described in detail later, by using a polyester resin that satisfies (iii), the mobility of the molecular chain can be increased and the molecular chain of the polyester resin can be easily oriented.
- the laminated polyester film of the present invention must satisfy the following (2).
- (2) a surface that satisfies (1), when measured at a Fourier transform infrared spectroscopy (FT-IR), and the spectral intensity r3 observed in 1018 cm -1, the spectrum intensity observed in 1602 cm -1 R3 calculated from r satisfies the following relationship. (Iii) 1.20 ⁇ R3 ⁇ 2.00
- R3 r3 / r.
- the resin constituting the layer having a surface satisfying (1) of the laminated polyester film of the present invention contains polyethylene terephthalate.
- polyethylene terephthalate Compared with polyethylene 2,6-naphthalenedicarboxylate, polyethylene terephthalate has a low glass transition temperature, and thus has a high mobility of molecular chains with respect to heat. Further, since the molecular structures of polyethylene 2,6-naphthalene dicarboxylate and polyethylene terephthalate are similar, the molecular chains are likely to cause physical interaction. Therefore, when polyethylene terephthalate is contained in polyethylene 2,6-naphthalenedicarboxylate, the mobility of the molecular chain of polyethylene 2,6-naphthalenedicarboxylate is increased due to the high mobility of the molecular chain of polyethylene terephthalate.
- the laminated polyester film of the present invention can be easily biaxially oriented. That is, by satisfying the above condition (iii), the above conditions (i) and (ii) are satisfied. In addition, the present inventors have found that, by satisfying the condition of (iii), the mobility of the molecular chain of the entire resin constituting the surface layer is increased and the processability of the film is improved.
- the value of R3 depends on the ratio of the contents of polyethylene 2,6-naphthalenedicarboxylate and polyethylene terephthalate in the resin constituting the layer having the surface satisfying (1) of the laminated polyester film of the present invention.
- polyethylene terephthalate and polyethylene 2,6-naphthalenedicarboxylate are used as a raw material for the resin constituting the layer having a surface satisfying (1) of the polyester film, and polyethylene terephthalate is used.
- polyethylene 2,6-naphthalenedicarboxylate is blended before melt film formation.
- the laminated polyester film of the present invention must satisfy the following (3).
- the melting point of the resin constituting the layer having a surface satisfying (1) and (2) is 260 ° C. or higher and 280 ° C. or lower.
- the melting point is obtained from 1st RUN of differential scanning calorimetry (DSC) by the measurement method described later. When two or more crystal melting peaks are observed, the peak top with the highest temperature is obtained. Is the melting point.
- the melting point of the resin constituting the A layer is less than 260 ° C., when the film is exposed to a high temperature, the heat resistance of the film surface affected by the highest temperature is not sufficient, and the film surface is likely to deteriorate due to heat. As a result, the heat resistance of the entire film is poor.
- the upper limit of the melting point of the resin constituting the A layer is preferably 275 ° C. or lower, and more preferably 270 ° C. or lower. By setting it as this range, it can be set as the film excellent in heat resistance.
- the method for setting the melting point of the resin constituting the A layer in the above range is, for example, using polyethylene terephthalate and polyethylene 2,6-naphthalenedicarboxylate as raw materials for the resin constituting the A layer, and using polyethylene terephthalate in the raw material. And the like, with respect to polyethylene 2,6-naphthalene dicarboxylate.
- the laminated polyester film of this invention satisfy
- the total thickness of the laminated polyester film is 120 ⁇ m or more and 500 ⁇ m or less.
- the polyester When the polyester is decomposed at a high temperature or in a moist heat atmosphere, the polyester proceeds from the film surface. Therefore, when the thickness of the whole film is 120 ⁇ m or more, the amount of polyester decomposed at high temperature or in a moist heat atmosphere is small with respect to the total amount of polyester constituting the film, and deterioration of the whole film can be suppressed.
- the conventional film having excellent heat resistance and heat and humidity resistance deteriorates the handleability of the film by increasing the film thickness. Therefore, when the total film thickness is 120 ⁇ m or more, the workability of the film, in particular, the bendability is inferior. Therefore, the film thickness could not be increased.
- the laminated polyester film of the present invention is not only excellent in heat resistance and moist heat resistance, but also has a good film processability (bendability and punchability) even when the total film thickness is 120 ⁇ m or more. Suitable for electrical insulation applications. If the thickness of the film exceeds 500 ⁇ m, it may be difficult to make the film biaxially oriented. The bendability can be evaluated by the bending strength (FE) based on JIS P-8115 (1994).
- Folding strength (FE) is obtained from the following formula (a) using the number of times N of folding until the film breaks due to deformation due to folding in a test based on JIS P-8115 (1994). .
- Formula (a) FE logN When FE is small, it is not preferable because it breaks during bending. If the FE is large, it is difficult to shape by bending. A preferable range is 4.1 ⁇ FE ⁇ 4.5. Moreover, satisfying the condition of (iii) is also a preferred embodiment for improving the bendability of the film.
- the difference between the glass transition temperature (Tg1) ° C. of the resin constituting the A layer and the glass transition temperature (Tg2) ° C. of the resin constituting the B layer satisfies the following relationship: Is preferred.
- a glass transition temperature is calculated
- stretching can be performed at a temperature lower than the glass transition temperature of the resin constituting the A layer.
- the orientation of the resin constituting the A layer can be easily imparted to the orientation.
- the above conditions (i) and (ii) are satisfied, and the heat resistance and heat and humidity resistance are improved. It can be set as the laminated polyester film excellent in.
- the resin constituting the B layer is preferably a polyester mainly composed of polyethylene terephthalate from the viewpoint of processability, mechanical properties, and heat resistance of the laminated polyester film.
- Polyester having polyethylene terephthalate as a main constituent is a ratio of terephthalic acid constituents in all dicarboxylic acid constituents of 95 mol% to 100 mol%, and a ratio of ethylene glycol constituents in all diol constituents is 95 mol% or more.
- the polyester is 100 mol% or less.
- the proportion of the terephthalic acid component in the total dicarboxylic acid component is 98 mol% or more and 100 mol% or less
- the proportion of the ethylene glycol component in the total diol component is 98 mol% or more and 100 mol% or less.
- fusing point of resin which comprises the said B layer is 253 degreeC or more and 258 degrees C or less. If it is lower than 253 ° C., the heat resistance may be inferior. If it exceeds 258 ° C., it becomes necessary to increase the stretching temperature, so that it becomes difficult to strengthen the orientation of the A layer, and the heat and moisture resistance and heat resistance may be inferior.
- the B layer is, when measured by Fourier transform infrared spectroscopy (FT-IR), R4 is less obtained from the spectral intensity r5 observed in spectral intensity r4 and 1372cm -1 which is observed 1388Cm -1 It is preferable to satisfy the relationship.
- (V) 0.95 ⁇ R4 ⁇ 1.05
- R4 r4 / r5.
- the laminated polyester film of the present invention preferably contains polyethylene terephthalate in the resin constituting the B layer.
- polyethylene terephthalate like polyethylene 2,6-naphthalate, is known to take two types of conformation of the methylene group portion of polyethylene terephthalate: Gauche type structure and trans type structure.
- the mold structure reflects the amorphous part of polyethylene terephthalate
- the trans structure reflects the crystal part due to the orientation of polyethylene terephthalate. That is, r4 reflects the Gauche structure derived from the amorphous part, and r5 reflects the trans structure derived from the crystalline part. It represents that there are many crystal parts with a regular structure, so that R4 is small.
- R4 When R4 is in the above range, it is preferable that the crystal portion and the amorphous portion are present in a well-balanced manner, and the mechanical properties of the film are improved in addition to heat resistance and heat and humidity resistance. Moreover, in order to make R4 into said range, making a film biaxially align on the conditions mentioned later is mentioned.
- the laminated polyester film of the present invention is preferably a film consisting of at least three layers in which both surface layers of the film are A layers. Since the A layer excellent in heat resistance and heat and moisture resistance is disposed on both surfaces of the film, the heat resistance and heat and moisture resistance of the entire laminated polyester film are improved, which is preferable. *
- a conventional polymerization method can be employed as a method for obtaining the polyester used in the present invention.
- it can be obtained by subjecting a dicarboxylic acid component such as terephthalic acid or a derivative thereof and a diol component such as ethylene glycol to a transesterification reaction or an esterification reaction by a known method, and then performing a melt polymerization reaction.
- the polyester obtained by the melt polymerization reaction may be subjected to a solid phase polymerization reaction at a temperature lower than the melting point of the polyester.
- you may add the mixture of phosphoric acid and an alkali metal phosphate from a viewpoint of improving the heat-and-moisture resistance of polyester.
- the addition amount of the mixture of phosphoric acid and alkali metal phosphate is 1.0 mol / t or more and 5.0 mol / t or less as the amount of phosphorus with respect to the polyester resin in order to reduce the influence of the polymerization delay due to the phosphorus compound. It is preferable.
- the laminated polyester film of the present invention can be obtained by a conventionally known production method, but the surface of the laminated polyester film is subjected to Fourier transform infrared spectroscopy (FT) by producing the stretching and heat treatment steps under the following conditions.
- FT Fourier transform infrared spectroscopy
- -IR is preferable because a laminated polyester film having a spectral intensity measured in the above range can be stably obtained.
- the laminated polyester film of the present invention can use a method (melt cast method) in which a dried raw material is heated and melted in an extruder as necessary, and is extruded onto a cast drum cooled from a die and processed into a sheet shape.
- a method melt cast method
- the raw material is dissolved in a solvent, and the solution is extruded from a die onto a support such as a cast drum or an endless belt to form a film, and then the solvent is dried and removed from the film layer to form a sheet.
- a method (solution casting method) or the like can also be used.
- an extruder is used for each layer constituting the laminated polyester film, the raw materials of each layer are melted, and these are melted in a joining device provided between the extrusion device and the die.
- a method is preferably used in which the layers are laminated, guided to a die, and extruded from the die onto a cast drum and processed into a sheet shape.
- the laminated sheet is closely cooled and solidified by static electricity on a drum cooled to a surface temperature of 10 ° C. or higher and 40 ° C. or lower to produce an unstretched sheet.
- the polyethylene terephthalate film of the present invention can be obtained by biaxially stretching this unstretched sheet.
- the time from melting in a nitrogen atmosphere to supplying chips to the extruder and extruding with a die is as short as possible.
- it is 30 minutes or less, more preferably 15 minutes.
- more preferably 5 minutes or less from the viewpoint of suppressing the increase in the amount of terminal carboxyl groups, and when using a plurality of types of polyester raw material, the polyester is copolymerized by a transesterification reaction in the extruder. It is preferable from the viewpoint of suppression.
- the amount of terminal carboxyl groups of the resin constituting the laminated polyester film of the present invention is 15 eq. From the viewpoint of improving the heat and moisture resistance.
- the temperature of the extruder at the time of melt extrusion with an extruder is from the viewpoint of suppressing an increase in the amount of terminal carboxyl groups, and when multiple types of polyester raw materials are used, the polyester is copolymerized by a transesterification reaction in the extruder. From the viewpoint of suppressing this, it is preferably less than 300 ° C, more preferably less than 290 ° C.
- the obtained unstretched sheet is biaxially stretched under the condition (5).
- the film At a temperature T1n satisfying the following formula (vi), the film is biaxially stretched in an area magnification of 12 times or more in the longitudinal direction (MD) of the film and the width direction (TD) of the film.
- Tg2 Glass transition temperature (° C.) of the resin constituting the B layer of the laminated polyester film
- a sequential biaxial stretching method in which stretching in the longitudinal direction (MD) of the film and stretching in the width direction of the film (direction perpendicular to the longitudinal direction of the film, TD) is performed, the longitudinal direction
- TD longitudinal direction
- Examples thereof include a simultaneous biaxial stretching method in which stretching in the direction and the width direction is simultaneously performed.
- T1n When the stretching temperature (T1n) is Tg2 or less, it cannot be stretched. Moreover, when T1n is in the above range, it becomes possible to impart orientation to the resin constituting the B layer of the laminated polyester film.
- a preferred embodiment of the laminated polyester film of the present invention is (iv) 30 ° C. ⁇ Tg 1 ⁇ Tg 2 ⁇ 40 ° C. as described above. Therefore, when the film satisfying (iv) is stretched under the condition satisfying (vi), T1n is the same temperature as the glass transition temperature (Tg1) of the resin constituting the A layer of the laminated polyester film, or The temperature is lower than Tg1. In the case of a polyester film composed of a single layer, it is usually impossible to provide orientation by stretching at or below the glass transition temperature of the polyester constituting the film.
- the layer A can be sufficiently stretched under the condition that the layer B in contact with the layer A can be sufficiently stretched. It can be stretched following this. Furthermore, since the resin constituting the A layer is stretched below the glass transition temperature of the resin constituting the A layer, it becomes easier to impart orientation. Moreover, in order to set it as the extending
- the thickness of the A layer (the total thickness of the A layer when the A layer is present on both surfaces of the film) T1 and the thickness of the B layer
- the ratio T1 / T2 of T2 is preferably 1/8 or more and 1/5 or less.
- either one of the surface layers of the laminated polyester film is configured to satisfy the condition (iii), and is stretched at a temperature satisfying the above (vi), whereby R1, R2 are (i), (ii) Can be met.
- the surface layer of either one of the laminated polyester films is configured to satisfy the condition (iii)
- the mobility of the polyester molecular chain constituting the layer is improved, and the orientation by stretching can be further increased.
- R3 is less than 1.20 (when the content of polyethylene terephthalate with respect to polyethylene 2,6-naphthalenedicarboxylate is low in the polyester resin constituting layer A), the mobility of the polyester molecular chain is insufficient, and the area magnification Even when the film is stretched by 12 times or more, the orientation by stretching cannot be imparted, so that the value of R1 exceeds 0.4 or the value of R2 becomes less than 1.25. Moreover, since the mobility of the polyester molecular chain is insufficient, when the draw ratio is increased to 13 times or more, the film forming property is deteriorated and the film cannot be formed.
- the value of R3 is increased by increasing the weight ratio of polyethylene terephthalate to polyethylene 2,6-naphthalenedicarboxylate in the resin constituting the A layer. And in connection with it, since the molecular mobility of resin which comprises A layer becomes high, it becomes easy to attach orientation. That is, R1 decreases and the value of R2 increases. On the other hand, as the weight ratio of polyethylene terephthalate to polyethylene 2,6-naphthalenedicarboxylate in the resin constituting the A layer is increased, the mobility of the molecular chains of the resin constituting the A layer increases, and the order is regular. It becomes difficult to have an array. That is, as a result of the decrease in crystallinity, it becomes difficult to achieve orientation.
- thermo treatment is performed at a temperature of Tg2 or more and less than the melting point of the laminated polyester film for 1 second or more and 30 seconds or less.
- the laminated polyester film of the present invention can be obtained by uniformly cooling slowly and then cooling to room temperature.
- the laminated polyester film of the present invention has excellent heat resistance, moist heat resistance, and processability. Therefore, the laminated film including the laminated polyester film of the present invention and having a surface satisfying (1) and (2) of the laminated polyester film on at least one outermost layer is an electrically insulating material, a magnetic recording material, a capacitor material, and a packaging material. It can be suitably used for building materials, photographic applications, graphic applications, thermal transfer applications, and the like.
- the surface satisfying (1) and (2) of the laminated polyester film of the present invention is provided for the purpose of imparting slipperiness, concealment and the like within a range not impairing the effects of the present invention.
- a layer by coating is provided on the surface of the laminated polyester film.
- the laminated polyester film of this invention can be obtained by the method of bonding with another layer so that the surface which satisfy
- organic particles, inorganic particles, dyes, and the like can be added to each layer constituting the film for the purpose of imparting easy slipperiness, concealing property and the like within a range not impairing the effects of the present invention.
- the film obtained by the present invention suppresses deterioration of physical properties even under high-temperature and high-humidity conditions, it uses HFC or the like as a refrigerant, as an electric insulating member for a motor in which the operating environment temperature of the compressor is higher than before. It can be used suitably.
- HFC or the like as a refrigerant, as an electric insulating member for a motor in which the operating environment temperature of the compressor is higher than before. It can be used suitably.
- A. Terminal carboxyl group content It is measured under the following conditions according to the method of Malice (references MJ Malice, F. Huizinga, Anal. Chim. Acta, 22 363 (1960)).
- polyester composition 2 g was dissolved in 50 mL of o-cresol / chloroform (weight ratio 7/3) at a temperature of 150 ° C., titrated with a 0.05N KOH / methanol solution, and the amount of terminal carboxyl groups was measured.
- Polyester 1t shown as eq./t in the table).
- the indicator at the time of titration uses phenol red, and the place where it changed from yellowish green to light red is set as the end point of titration.
- the peak top temperature at the crystal melting peak which is the endothermic peak, is determined, and this is defined as the melting point (° C.).
- the temperature at the peak top with the highest temperature is taken as the melting point.
- Tg1 measurement only the resin constituting the surface layer is cut from the laminated polyester film using a microtome and used for the measurement.
- Tg2 measurement only the resin constituting the layer in contact with the surface layer is further cut out from the film after the thickness of the resin constituting the surface layer is cut from the laminated polyester film using a microtome, and used for measurement.
- FT-IR Fourier Transform Infrared Spectroscopy
- the surface layer of the film is closely attached to the medium crystal and measurement is performed.
- the contact between the medium crystal and the sample is performed by applying pressure using a jig attached to the apparatus.
- the pressure is increased while observing the spectrum of the sample, and measurement is performed when the spectrum shape does not change due to the pressure.
- the surface of the film after the thickness of the resin constituting the surface layer has been trimmed from the laminated polyester film using a microtome is closely attached to the medium crystal. carry out.
- the layer provided by the coating is removed and subjected to measurement.
- the film cut out in the same manner is treated with a pressure cooker manufactured by Tabai Espec Co., Ltd. under high-humidity heat conditions of a temperature of 125 ° C. and a relative humidity of 100% RH, and then the elongation at break is measured.
- n 5 and it measures about each of the longitudinal direction of a film, and the width direction, and let the average value be the breaking elongation E1.
- the elongation retention is calculated by the following equation (a).
- the treatment time is changed by one hour, and the treatment time at which the elongation retention is 50% or less is defined as the elongation half life.
- Elongation retention (%) E1 / E0 ⁇ 100 From the obtained elongation half-life, the heat-and-moisture resistance of the film was determined as follows. When elongation half-life is 70 hours or more: A When the elongation half-life is 60 hours or more and less than 70 hours: B When the elongation half-life is 51 hours or more and less than 60 hours: C When elongation half-life is less than 51 hours: D A, B, and C are good, and A is the best among them.
- the elongation retention is calculated by the following equation (b).
- the treatment time is changed by one hour, and the treatment time at which the strength retention is 50% or less is defined as the strength half life.
- (B) Strength retention (%) S1 / S0 ⁇ 100 From the obtained elongation half-life, the heat resistance of the film was determined as follows.
- Laminated polyester film thickness ( ⁇ m) The film thickness was measured at any five locations using a dial gauge according to JIS K7130 (1992) A-2 method with 10 films stacked. The average value was divided by 10 to obtain the film thickness.
- Thickness ( ⁇ m) of each layer of laminated polyester film A film cross section is cut out with a microtome in a direction parallel to the film width direction and in a direction perpendicular to the film thickness direction. The cross section is observed with a scanning electron microscope at a magnification of 5000 times to determine the thickness ratio of each layer. The thickness of each layer is calculated from the obtained lamination ratio and the above-described film thickness.
- the folding strength FE is calculated from the average value N by the following formula (c), and the bendability is evaluated.
- (C) FE logN FE ⁇ 4.1: Poor bendability (described as “poor” in the table) 4.1 ⁇ FE ⁇ 4.5: Good bendability (described as fine in the table) 4.5 ⁇ FE: Poor bending property (described as “poor” in the table) J. et al.
- Punching property A laminated polyester film is punched into a No. 5 type dumbbell shape described in JIS K-6251 using a test piece punching machine manufactured by Kobunshi Keiki Co., Ltd. The number of sheets M in which the end face is cracked or peeled when punching 10 sheets one by one is counted, and the punchability is evaluated. 0 ⁇ M ⁇ 2: Punchability A 3 ⁇ M ⁇ 5: Punchability B 6 ⁇ N ⁇ 10: Punchability C A is the best and C is the worst.
- the direction having the maximum refractive index in the film is regarded as the longitudinal direction
- the direction orthogonal to the longitudinal direction is regarded as the width direction.
- the direction of the maximum refractive index in the film may be obtained by measuring the refractive index in all directions of the film with a refractometer, and the slow axis direction may be determined by a phase difference measuring device (birefringence measuring device) or the like. It may be obtained by deciding.
- PET-A Polymerization was carried out in a conventional manner using terephthalic acid and ethylene glycol as raw materials and antimony trioxide as a catalyst to obtain PET-B.
- the obtained PET-B had a glass transition temperature of 81 ° C., a melting point of 255 ° C., an intrinsic viscosity of 0.68, and a terminal carboxyl group content of 20 eq. / T.
- PET-B was solid-phase polymerized by a conventional method to obtain PET-A.
- the obtained PET-A had a glass transition temperature of 82 ° C., a melting point of 255 ° C., an intrinsic viscosity of 0.85, and a terminal carboxyl group content of 11 eq. / T.
- PEN-A A transesterification reaction was carried out using dimethyl 2,6-naphthalenedicarboxylate and ethylene glycol as raw materials and manganese acetate as a catalyst. After the transesterification reaction, PEN-A was obtained by a conventional method using antimony trioxide as a catalyst. The obtained PEN-A had a glass transition temperature of 124 ° C., a melting point of 265 ° C., an intrinsic viscosity of 0.62, and a terminal carboxyl group concentration of 25 eq. / T.
- PET / NA Transesterification was performed using 100 parts by mass of dimethyl 2,6-naphthalenedicarboxylate, 10 parts by mass of dimethyl terephthalate and ethylene glycol as raw materials and using manganese acetate as a catalyst. After completion of the transesterification reaction, a copolyester PET / NA was obtained by a conventional method using antimony trioxide as a catalyst. The obtained PET / NA has a glass transition temperature of 120 ° C., a melting point of 255 ° C., an intrinsic viscosity of 0.62, and a terminal carboxyl group concentration of 20 eq. / T.
- PET / NB Transesterification was performed using 100 parts by mass of dimethyl 2,6-naphthalenedicarboxylate, 20 parts by mass of dimethyl terephthalate and ethylene glycol as raw materials and using manganese acetate as a catalyst. After completion of the transesterification reaction, a copolyester PET / NB was obtained by a conventional method using antimony trioxide as a catalyst. The obtained PET / NB has a glass transition temperature of 115 ° C., a melting point of 250 ° C., an intrinsic viscosity of 0.62, and a terminal carboxyl group concentration of 20 eq. / T.
- PET / IA The transesterification reaction was carried out using 97 parts by mass of dimethyl terephthalate, 3 parts by mass of dimethyl isophthalate and ethylene glycol as raw materials and using manganese acetate as a catalyst. After completion of the transesterification reaction, a copolyester ⁇ was obtained by a conventional method using antimony trioxide as a catalyst. The obtained polyester ⁇ was solid-phase polymerized by a conventional method to obtain PET / IA.
- PET / IA has a glass transition temperature of 80 ° C., a melting point of 249 ° C., an intrinsic viscosity of 0.82, and a terminal carboxyl group concentration of 13 eq. / T.
- PET-C and PET-D Polymerization was carried out using terephthalic acid and ethylene glycol as raw materials and antimony trioxide as a catalyst. Simultaneously with antimony trioxide, a solution of phosphoric acid and sodium dihydrogen phosphate dihydrate dissolved in ethylene glycol was added. Phosphoric acid was added in an amount corresponding to 2.0 mol / t with respect to PET, and sodium dihydrogen phosphate dihydrate was added in an amount corresponding to 1.7 mol / t with respect to PET.
- PET-D had a glass transition temperature of 81 ° C., a melting point of 255 ° C., an intrinsic viscosity of 0.68, and a terminal carboxyl group content of 20 eq. / T.
- PET-D was solid-phase polymerized by a conventional method to obtain PET-C.
- the obtained PET-C had a glass transition temperature of 82 ° C., a melting point of 255 ° C., an intrinsic viscosity of 0.85, and a terminal carboxyl group content of 11 eq. / T.
- PEN-B A transesterification reaction was carried out using dimethyl 2,6-naphthalenedicarboxylate and ethylene glycol as raw materials and manganese acetate as a catalyst. After the transesterification reaction, polymerization was carried out using antimony trioxide as a catalyst. Simultaneously with antimony trioxide, a solution of phosphoric acid and sodium dihydrogen phosphate dihydrate dissolved in ethylene glycol was added. Phosphoric acid was added so as to be equivalent to 2.0 mol / t with respect to PET, and sodium dihydrogen phosphate dihydrate was added so as to correspond to 1.7 mol / t with respect to PET, and the polymerization reaction was allowed to proceed. Got. The obtained PEN-B had a glass transition temperature of 124 ° C., a melting point of 265 ° C., an intrinsic viscosity of 0.62, and a terminal carboxyl group concentration of 25 eq. / T.
- Example 1 As a resin constituting the surface layer, 95 parts by mass of PEN-A and 5 parts by mass of PET-A were blended, vacuum-dried at 160 ° C. for 2 hours, and then charged into the extruder 1. Further, 100 parts by mass of PET-A as a resin constituting a layer in contact with the surface layer was vacuum-dried at 160 ° C. for 2 hours, and then charged into the extruder 2. Each raw material was melted in an extruder, and the resin charged into the extruder 1 was merged by a merger so as to be both surface layers of the film, and extruded into a casting drum shape to produce a laminated sheet having a three-layer structure.
- the sheet is preheated with a heated roll group, then stretched 3.3 times in the longitudinal direction (MD direction) at a temperature of 95 ° C., and then cooled with a roll group at a temperature of 25 ° C. to be a uniaxially stretched film.
- MD direction longitudinal direction
- roll group a temperature of 25 ° C.
- the obtained uniaxially stretched film was stretched 3.7 times in the width direction (TD direction) perpendicular to the longitudinal direction in a heating zone at a temperature of 110 ° C. in the tenter while holding both ends with clips.
- a heat treatment was performed for 10 seconds at a temperature of 220 ° C. in a heat treatment zone in the tenter, and a relaxation treatment was further performed in the 4% width direction at a temperature of 220 ° C.
- the film was gradually cooled in a cooling zone and wound up to obtain a laminated polyester film having a thickness of 125 ⁇ m.
- a laminated polyester film having a thickness of 125 ⁇ m.
- Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
- Examples 2 to 4, 9 to 16, 25, 26 A laminated polyester film in the same manner as in Example 1 except that the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer, the thickness of the laminated polyester film, and the thickness of each layer were changed as described in the table. Got. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
- Example 5 to 8 A laminated polyester film was obtained in the same manner as in Example 1 except that the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer and the stretching process of the laminated polyester film were changed as described in the table. . Each characteristic of the obtained film is shown in the table. By increasing the draw ratio, R1 and R2 became more preferable ranges, and a film excellent in heat resistance and moist heat resistance was obtained.
- Example 17 a laminated polyester film was obtained in the same manner as in Example 1, except that the laminated structure of the film was two layers and the thickness of each layer of the laminated polyester film was changed as described in the table.
- Example 18 to 20 laminated polyester films were obtained in the same manner as in Example 17 except that the resin constituting the A layer was changed as described in the table. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
- Example 21 to 24 A laminated polyester film was obtained in the same manner as in Example 1 except that the thickness of the surface layer and the thickness of the laminated polyester film were changed. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
- Example 27 A laminated polyester film was obtained in the same manner as in Example 4 except that the raw material used for the B layer was PET / IA and the stretching conditions were changed as shown in the table. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
- Example 29 A laminated polyester film was obtained in the same manner as in Example 4 except that the raw material used for the B layer was PET-B. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
- Example 5 A laminated polyester film was obtained in the same manner as in Example 1 except that the raw material used for the resin constituting the surface layer was PET / NA and PET / NB. Each characteristic of the laminated polyester film is shown in the table. Since a copolymer is used, it is difficult to impart orientation by stretching, the values of R1 and R2 do not satisfy (i) and (ii), and the melting point of the resin constituting the surface layer is less than 260 ° C. Therefore, it turned out that it is inferior to heat resistance and heat-and-moisture resistance.
- the extrusion temperature of the resin constituting the surface layer is 300 ° C., the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer, the thickness of the laminated polyester film, the thickness of each layer, and the stretching process of the laminated polyester film
- a laminated polyester film was obtained in the same manner as in Example 1 except that it was as described in the table.
- the extrusion temperature of the resin constituting the surface layer is high, the copolymerization proceeds by transesterification of the resins constituting the surface layer, it is difficult to impart orientation by stretching, and the values of R1 and R2 are (i) (ii) It did not satisfy
- Example 30 to 36 Example except that the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer, the thickness of the laminated polyester film, the thickness of each layer, and the stretching process of the laminated polyester film were changed as described in the table 1 to obtain a laminated polyester film.
- Each characteristic of the obtained laminated polyester film is shown in the table.
- the thickness of the film was 120 ⁇ m or less, it was found that by reducing the ratio of the thickness of the A layer to the B layer, the resin constituting the A layer was easily oriented, and the heat and heat resistance and heat resistance were excellent.
- the film thickness was thin, the workability (punchability) was slightly inferior to that of Example 1, but the level was satisfactory.
- Example 37 and 38 Using the laminated polyester film of Example 35, paste Torayna (registered trademark) 3000 manufactured by Toray Industries, Inc. on the B layer side with an adhesive layer so that the A layer of Example 35 is the outermost layer. Combined.
- the configuration was the film / adhesive layer / tolerina of Example 35.
- the adhesive layer was adjusted with a gravure coater so that the thickness after drying epoxy adhesive chemit TE2301 manufactured by Toray Fine Chemical was 3 ⁇ m.
- the thickness of Toray Industries, Inc.'s Torelina was 100 ⁇ m in Example 37 and 15 ⁇ m in Example 38.
- the properties of the obtained film are shown in the table. It was found to be excellent in heat resistance, moist heat resistance and processability.
- Example 39 Using the film of Example 35, both layers of Torayna (registered trademark) 3000 (thickness 100 ⁇ m) manufactured by Toray Industries, Inc. are bonded via an adhesive layer so that layer A of Example 35 is the outermost layer. It was.
- the configuration was the film of Example 35 / adhesive layer / tolerina / adhesive layer / film of Example 35.
- the properties of the obtained film are shown in the table. It was found to be excellent in heat resistance, moist heat resistance and processability.
- Example 40 After uniaxially stretching in the longitudinal direction of the film, the same coating as in Example 1 was applied except that the following coating agent was applied to one surface of the film with a coating thickness of about 8 ⁇ m using a bar coat for the purpose of imparting easy slipperiness. Thus, a laminated polyester film was obtained.
- a coating agent water is used as a coating liquid, and 100 parts by weight of Bernock (registered trademark) 310E manufactured by DIC Corporation is used. Colloidal silica snowtex (registered trademark) ST-50 manufactured by Nissan Chemical Industries, Ltd. is used. The concentration was adjusted to 5 parts by weight, and the solid content weight was 5% by weight. The properties of the obtained film are shown in the table. As in Example 1, it was found that heat resistance, heat and humidity resistance, and workability were excellent.
- Example 41 A laminated polyester film was obtained in the same manner as in Example 1 except that PEN-B and PET-C were used as the resin constituting the surface layer, and PET-C was used as the resin constituting the layer in contact with the surface layer. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability. Since PEN-B is used in place of PEN-A and PET-C is used in place of PET-A, it can be seen that the heat and heat resistance is excellent.
- Example 42 A laminated polyester film was obtained in the same manner as in Example 1 except that PEN-A and PET-D were used as the resin constituting the surface layer, and PET-A was used as the resin constituting the layer in contact with the surface layer. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
- Example 15 Example except that the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer, the thickness of the laminated polyester film, the thickness of each layer, and the stretching process of the laminated polyester film were changed as described in the table 1 to obtain a laminated polyester film.
- Each characteristic of the obtained laminated polyester film is shown in the table. Since the area ratio at the time of stretching exceeds 17 times, the molecular chains of the resin constituting the surface layer are regularly arranged, and the number of crystal parts increases, so the values of R1 and R2 do not satisfy (i) (ii) and workability is improved. Inferior.
- the present invention it is possible to provide a polyester film that is excellent in heat resistance, heat and humidity resistance, and processability and that satisfies long-term use. Since the film obtained by the present invention suppresses deterioration of physical properties even under high temperature and high humidity conditions, a laminated polyester film that can withstand long-term use even when used as an electric insulating member of a motor using a refrigerant composed of HFC Can be provided.
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Abstract
Description
[I]以下の(1)から(3)の要件を満たす、少なくとも2層からなる積層ポリエステルフィルム。
(1)少なくとも一方の表面が、フーリエ変換型赤外分光法(FT-IR)にて測定したとき、1452cm-1に観察されるスペクトル強度r1と、1332cm-1に観察されるスペクトル強度r2と、1602cm-1に観察されるスペクトル強度rから求められるR1、R2が以下の関係を満たすこと。
(i)0.2≦R1≦0.4
(ii)1.25≦R2≦1.50
ここで、R1=r1/r、R2=r2/r
(2)(1)を満たす表面が、フーリエ変換型赤外分光法(FT-IR)にて測定したとき、1018cm-1に観察されるスペクトル強度r3と、1602cm-1に観察されるスペクトル強度rから求められるR3が以下の関係を満たすこと。
(iii) 1.20≦R3≦2.00
ここで、R3=r3/r
(3)(1)(2)を満たす表面を有する層(該層をA層とする)を構成する樹脂の融点が260℃以上280℃以下であること。
[II]以下の(4)を満たす、[I]に記載の積層ポリエステルフィルム。
(4)フィルムの総厚みTが120μm以上500μm以下であること。
[III]上記A層を構成する樹脂のガラス転移温度(Tg1)℃と、上記A面を有する層に隣接する層(該層をB層とする)を構成する樹脂のガラス転移温度(Tg2)℃との差が以下の関係を満たす[I]または[II]に記載の積層ポリエステルフィルム。
(iv)30℃≦Tg1-Tg2≦40℃
[IV]上記B層が、フーリエ変換型赤外分光法(FT-IR)にて測定したとき、1388cm-1に観察されるスペクトル強度r4と1372cm-1に観察されるスペクトル強度r5から求められるR4が以下の関係を満たす[I]から[III]のいずれかに記載の積層ポリエステルフィルム。
(v)0.95≦R4≦1.05
ここで、R4=r4/r5
[V]フィルムの両側表層がA層からなる、少なくとも3層からなる[I]から[IV]のいずれかに記載の積層ポリエステルフィルム。
[VI]上記B層を構成する樹脂の融点が253℃以上258℃以下である[I]から[V]のいずれかに記載の積層ポリエステルフィルム。
[VII]積層ポリエステルフィルムを構成するポリエステル樹脂の末端カルボキシル基量が15eq./t以下である[I]から[VI]のいずれかに記載の積層ポリエステルフィルム。
[VIII]モーターの電気絶縁部材として用いられる請求項[I]から[VII]のいずれかに記載の積層ポリエステルフィルム。
[IX][I]から[VIII]のいずれかに記載の積層ポリエステルフィルムを含み、積層ポリエステルフィルムの(1)(2)を満たす表面を少なくとも片側の最表層に有する積層フィルム。 In order to solve the above problems, the present invention has the following configuration. That is,
[I] A laminated polyester film comprising at least two layers that satisfies the following requirements (1) to (3).
(1) at least one surface, when measured by Fourier transform infrared spectroscopy (FT-IR), and the spectral intensity r1 observed in 1452Cm -1, the spectrum intensity r2 observed in 1332 cm -1 R1 and R2 obtained from the spectral intensity r observed at 1602 cm −1 satisfy the following relationship.
(I) 0.2 ≦ R1 ≦ 0.4
(Ii) 1.25 ≦ R2 ≦ 1.50
Here, R1 = r1 / r, R2 = r2 / r
(2) a surface that satisfies (1), when measured at a Fourier transform infrared spectroscopy (FT-IR), and the spectral intensity r3 observed in 1018 cm -1, the spectrum intensity observed in 1602 cm -1 R3 calculated from r satisfies the following relationship.
(Iii) 1.20 ≦ R3 ≦ 2.00
Where R3 = r3 / r
(3) The melting point of the resin constituting the layer having a surface satisfying (1) and (2) (this layer is referred to as layer A) is 260 ° C. or higher and 280 ° C. or lower.
[II] The laminated polyester film according to [I], which satisfies the following (4).
(4) The total thickness T of the film is 120 μm or more and 500 μm or less.
[III] Glass transition temperature (Tg1) ° C. of the resin constituting the A layer and glass transition temperature (Tg2) of the resin constituting the layer adjacent to the layer having the A plane (this layer is referred to as B layer) The laminated polyester film according to [I] or [II], in which a difference from ° C. satisfies the following relationship.
(Iv) 30 ° C. ≦ Tg1-Tg2 ≦ 40 ° C.
[IV] The layer B is obtained from a spectral intensity r4 observed at 1388 cm −1 and a spectral intensity r5 observed at 1372 cm −1 when measured by Fourier transform infrared spectroscopy (FT-IR). The laminated polyester film according to any one of [I] to [III], wherein R4 satisfies the following relationship.
(V) 0.95 ≦ R4 ≦ 1.05
Here, R4 = r4 / r5
[V] The laminated polyester film according to any one of [I] to [IV], in which both surface layers of the film are composed of A layers and are composed of at least three layers.
[VI] The laminated polyester film according to any one of [I] to [V], wherein the resin constituting the B layer has a melting point of 253 ° C. or higher and 258 ° C. or lower.
[VII] The amount of terminal carboxyl groups of the polyester resin constituting the laminated polyester film is 15 eq. The laminated polyester film according to any one of [I] to [VI], which is / t or less.
[VIII] The laminated polyester film according to any one of [I] to [VII], which is used as an electric insulating member of a motor.
[IX] A laminated film including the laminated polyester film according to any one of [I] to [VIII] and having a surface satisfying (1) and (2) of the laminated polyester film on at least one outermost layer.
(1)少なくとも一方の表面が、フーリエ変換型赤外分光法(FT-IR)にて測定したとき、1452cm-1に観察されるスペクトル強度r1と、1332cm-1に観察されるスペクトル強度r2と、1602cm-1に観察されるスペクトル強度rから求められるR1、R2が以下の関係を満たす。
(i)0.2≦R1≦0.4
(ii) 1.25≦R2≦1.50
ここで、R1=r1/r、R2=r2/r。 The laminated polyester film of the present invention must satisfy the following (1).
(1) at least one surface, when measured by Fourier transform infrared spectroscopy (FT-IR), and the spectral intensity r1 observed in 1452Cm -1, the spectrum intensity r2 observed in 1332 cm -1 R1 and R2 obtained from the spectral intensity r observed at 1602 cm −1 satisfy the following relationship.
(I) 0.2 ≦ R1 ≦ 0.4
(Ii) 1.25 ≦ R2 ≦ 1.50
Here, R1 = r1 / r, R2 = r2 / r.
(2)(1)を満たす表面が、フーリエ変換型赤外分光法(FT-IR)にて測定したとき、1018cm-1に観察されるスペクトル強度r3と、1602cm-1に観察されるスペクトル強度rから求められるR3が以下の関係を満たすこと。
(iii) 1.20≦R3≦2.00
ここで、R3=r3/r。 Moreover, the laminated polyester film of the present invention must satisfy the following (2).
(2) a surface that satisfies (1), when measured at a Fourier transform infrared spectroscopy (FT-IR), and the spectral intensity r3 observed in 1018 cm -1, the spectrum intensity observed in 1602 cm -1 R3 calculated from r satisfies the following relationship.
(Iii) 1.20 ≦ R3 ≦ 2.00
Here, R3 = r3 / r.
(3)(1)(2)を満たす表面を有する層(該層をA層とする)を構成する樹脂の融点が260℃以上280℃以下である。なお、本発明において、融点は、後述する測定方法により示差走査型熱量測定(DSC)の1stRUNから求められるものであり、2以上の結晶融解ピークが観測される場合は、最も温度が高いピークトップの温度を融点とする。 Moreover, the laminated polyester film of the present invention must satisfy the following (3).
(3) The melting point of the resin constituting the layer having a surface satisfying (1) and (2) (this layer is referred to as layer A) is 260 ° C. or higher and 280 ° C. or lower. In the present invention, the melting point is obtained from 1st RUN of differential scanning calorimetry (DSC) by the measurement method described later. When two or more crystal melting peaks are observed, the peak top with the highest temperature is obtained. Is the melting point.
(4)積層ポリエステルフィルム全体の厚みが120μm以上500μm以下であること。 Moreover, it is preferable that the laminated polyester film of this invention satisfy | fills following (4).
(4) The total thickness of the laminated polyester film is 120 μm or more and 500 μm or less.
式(a)FE=logN
FEが小さいと、折り曲げ加工時に破断して好ましくない。FEが大きいと、折り曲げによって形状をつけることが難しい。好ましい範囲としては、4.1≦FE≦4.5である。また、(iii)の条件を満足することも、フィルムの折り曲げ性を向上させるための好ましい実施形態である。 When the polyester is decomposed at a high temperature or in a moist heat atmosphere, the polyester proceeds from the film surface. Therefore, when the thickness of the whole film is 120 μm or more, the amount of polyester decomposed at high temperature or in a moist heat atmosphere is small with respect to the total amount of polyester constituting the film, and deterioration of the whole film can be suppressed. In addition, the conventional film having excellent heat resistance and heat and humidity resistance deteriorates the handleability of the film by increasing the film thickness. Therefore, when the total film thickness is 120 μm or more, the workability of the film, in particular, the bendability is inferior. Therefore, the film thickness could not be increased. Moreover, when the thickness of the film is less than 120 μm, there is a problem that punchability is deteriorated in the workability of the film. However, the laminated polyester film of the present invention is not only excellent in heat resistance and moist heat resistance, but also has a good film processability (bendability and punchability) even when the total film thickness is 120 μm or more. Suitable for electrical insulation applications. If the thickness of the film exceeds 500 μm, it may be difficult to make the film biaxially oriented. The bendability can be evaluated by the bending strength (FE) based on JIS P-8115 (1994). Folding strength (FE) is obtained from the following formula (a) using the number of times N of folding until the film breaks due to deformation due to folding in a test based on JIS P-8115 (1994). .
Formula (a) FE = logN
When FE is small, it is not preferable because it breaks during bending. If the FE is large, it is difficult to shape by bending. A preferable range is 4.1 ≦ FE ≦ 4.5. Moreover, satisfying the condition of (iii) is also a preferred embodiment for improving the bendability of the film.
上記条件を満たす場合、後述する方法で積層ポリエステルフィルムを二軸延伸せしめた場合、上記A層に対してはA層を構成する樹脂のガラス転移温度以下で、上記B層に対してはB層を構成する樹脂のガラス転移温度以上の温度で延伸することが可能となる。該条件では、通常ではB層を構成する樹脂を延伸することは出来るが、上記A層を構成する樹脂を延伸することは出来ない。しかしながら、本発明のフィルムをA層とB層が隣接している積層ポリエステルフィルムとすることで、A層を構成する樹脂が、B層を構成する樹脂が延伸されるのに追随して延伸されることにより、A層を構成する樹脂のガラス転移温度以下で延伸が可能となる。A層を構成する樹脂のガラス転移温度以下で延伸を行うことにより、A層を構成する樹脂により配向を付与せしめやすくなる結果、上記(i)(ii)の条件を満たし、耐熱性、耐湿熱性に優れた積層ポリエステルフィルムとすることができる。 (Iv) 30 ° C. ≦ Tg1-Tg2 ≦ 40 ° C.
When the above conditions are satisfied, when the laminated polyester film is biaxially stretched by the method described later, the glass transition temperature of the resin constituting the A layer is below the A layer, and the B layer is the B layer. It becomes possible to stretch at a temperature equal to or higher than the glass transition temperature of the resin constituting the. Under these conditions, the resin constituting the B layer can be usually stretched, but the resin constituting the A layer cannot be stretched. However, by forming the film of the present invention into a laminated polyester film in which the A layer and the B layer are adjacent, the resin constituting the A layer is stretched following the stretching of the resin constituting the B layer. Thus, stretching can be performed at a temperature lower than the glass transition temperature of the resin constituting the A layer. By stretching below the glass transition temperature of the resin constituting the A layer, the orientation of the resin constituting the A layer can be easily imparted to the orientation. As a result, the above conditions (i) and (ii) are satisfied, and the heat resistance and heat and humidity resistance are improved. It can be set as the laminated polyester film excellent in.
(v)0.95≦R4≦1.05
ここで、R4=r4/r5。 The B layer is, when measured by Fourier transform infrared spectroscopy (FT-IR), R4 is less obtained from the spectral intensity r5 observed in spectral intensity r4 and 1372cm -1 which is observed 1388Cm -1 It is preferable to satisfy the relationship.
(V) 0.95 ≦ R4 ≦ 1.05
Here, R4 = r4 / r5.
(5)下記(vi)式を満たす温度T1nにて、フィルムの長手方向(MD)とフィルムの幅方向(TD)に面積倍率12倍以上に二軸延伸する。
(vi)Tg2≦T1n≦Tg2+30℃
Tg2:積層ポリエステルフィルムのB層を構成する樹脂のガラス転移温度(℃)
二軸延伸する方法としては、フィルムの長手方向(MD)とフィルムの幅方向(フィルムの長手方向に垂直な方向、TD)の延伸とを分離して行う逐次二軸延伸方法の他に、長手方向と幅方向の延伸を同時に行う同時二軸延伸方法が挙げられる。 The obtained unstretched sheet is biaxially stretched under the condition (5).
(5) At a temperature T1n satisfying the following formula (vi), the film is biaxially stretched in an area magnification of 12 times or more in the longitudinal direction (MD) of the film and the width direction (TD) of the film.
(Vi) Tg2 ≦ T1n ≦ Tg2 + 30 ° C.
Tg2: Glass transition temperature (° C.) of the resin constituting the B layer of the laminated polyester film
As a method of biaxial stretching, in addition to a sequential biaxial stretching method in which stretching in the longitudinal direction (MD) of the film and stretching in the width direction of the film (direction perpendicular to the longitudinal direction of the film, TD) is performed, the longitudinal direction Examples thereof include a simultaneous biaxial stretching method in which stretching in the direction and the width direction is simultaneously performed.
[特性の評価方法]
A.末端カルボキシル基量
Mauliceの方法に準じて以下の条件よって測定する(文献M.J.Maulice, F. Huizinga, Anal.Chim.Acta,22 363(1960))。ポリエステル組成物2gをo-クレゾール/クロロホルム(重量比7/3)50mLに温度150℃にて溶解し、0.05NのKOH/メタノール溶液によって滴定し、末端カルボキシル基量を測定し、eq./ポリエステル1tの値で示す(表中では、eq./tと記載する)。なお、滴定時の指示薬はフェノールレッドを用いて、黄緑色から淡紅色に変化したところを滴定の終点とする。 Since the film obtained by the present invention suppresses deterioration of physical properties even under high-temperature and high-humidity conditions, it uses HFC or the like as a refrigerant, as an electric insulating member for a motor in which the operating environment temperature of the compressor is higher than before. It can be used suitably.
[Characteristic evaluation method]
A. Terminal carboxyl group content It is measured under the following conditions according to the method of Malice (references MJ Malice, F. Huizinga, Anal. Chim. Acta, 22 363 (1960)). 2 g of the polyester composition was dissolved in 50 mL of o-cresol / chloroform (weight ratio 7/3) at a temperature of 150 ° C., titrated with a 0.05N KOH / methanol solution, and the amount of terminal carboxyl groups was measured. / Polyester 1t (shown as eq./t in the table). In addition, the indicator at the time of titration uses phenol red, and the place where it changed from yellowish green to light red is set as the end point of titration.
試料を、JIS K-7121(1999)に基づいた方法により、セイコー電子工業(株)製示差走査熱量測定装置“ロボットDSC-RDC220”を、データ解析にはディスクセッション“SSC/5200”を用いて、下記の要領にて、測定を実施した。
サンプルパンに試料を5mgずつ秤量し、試料を25℃から300℃まで20℃/分の昇温速度で加熱した(1stRUN)。1stRUNの示差走査熱量測定チャート(縦軸を熱エネルギー、横軸を温度とする)を得る。当該1stRunの示差走査熱量測定チャートの、吸熱ピークである結晶融解ピークにおけるピークトップの温度を求め、これを融点(℃)とする。2以上の結晶融解ピークが観測される場合は、最も温度が高いピークトップの温度を融点とする。 B. Melting point (° C) of resin constituting each layer
Using a method based on JIS K-7121 (1999), a differential scanning calorimeter “Robot DSC-RDC220” manufactured by Seiko Denshi Kogyo Co., Ltd. and a disk session “SSC / 5200” for data analysis were used. The measurement was carried out in the following manner.
The sample was weighed in a sample pan by 5 mg, and the sample was heated from 25 ° C. to 300 ° C. at a heating rate of 20 ° C./min (1st RUN). A 1st RUN differential scanning calorimetry chart (the vertical axis is thermal energy and the horizontal axis is temperature) is obtained. In the differential scanning calorimetry chart of 1stRun, the peak top temperature at the crystal melting peak, which is the endothermic peak, is determined, and this is defined as the melting point (° C.). When two or more crystal melting peaks are observed, the temperature at the peak top with the highest temperature is taken as the melting point.
JIS K7121(1999)に準じて、セイコー電子工業(株)製示差走査熱量測定装置”ロボットDSC-RDC220”を、データ解析にはディスクセッション”SSC/5200”を用いて、下記の要領にて、測定を実施する。 C. Glass transition temperature Tg1 of the resin constituting the surface layer, glass transition temperature Tg2 (° C.) of the resin constituting the layer in contact with the surface layer
In accordance with JIS K7121 (1999), the differential scanning calorimeter “Robot DSC-RDC220” manufactured by Seiko Denshi Kogyo Co., Ltd. and the disk session “SSC / 5200” for data analysis were used as follows. Perform the measurement.
(株)パーキンエルマー製のFrontier FT-IR(Spectrum One 400)を用い、UATR IRユニットを使用して、媒質結晶をダイヤモンド/ZnSeとして、減衰全反射法(ATR法)によってスペクトル強度を測定する。分光器の分解能は1cm-1、スペクトルの積算回数は16回として測定する。スペクトル強度は、各波長での吸光度(arb.unit)とする。 D. Fourier Transform Infrared Spectroscopy (FT-IR) Spectral Intensity Using a Frontier FT-IR (Spectrum One 400) manufactured by PerkinElmer Co., Ltd. and using a UATR IR unit, the medium crystal is attenuated as diamond / ZnSe. The spectral intensity is measured by the total reflection method (ATR method). The spectroscope has a resolution of 1 cm −1 and the spectrum is integrated 16 times. The spectral intensity is the absorbance (arb. Unit) at each wavelength.
積層ポリエステルフィルムを1cm×20cmの大きさに、長辺がフィルムの長手方向・幅方向に平行となるようにそれぞれ切り出し、ASTM-D882(1997)に基づいて、チャック間5cm、引っ張り速度300mm/分にて引っ張ったときの破断伸度を測定する。なお、サンプル数はn=5とし、また、フィルムの長手方向、幅方向のそれぞれについて測定した後、それらの平均値を求め、これをフィルムの破断伸度E0とする。 E. Heat-and-moisture resistance of laminated polyester film The laminated polyester film is cut into a size of 1 cm × 20 cm and the long side is parallel to the longitudinal direction and the width direction of the film, respectively, and 5 cm between chucks based on ASTM-D882 (1997). The elongation at break when measured at a pulling speed of 300 mm / min is measured. The number of samples is n = 5, and after measuring in the longitudinal direction and the width direction of the film, the average value thereof is obtained, and this is defined as the elongation at break E0 of the film.
(a) 伸度保持率(%)=E1/E0×100
得られた伸度半減期から、フィルムの耐湿熱性を以下のように判定した。
伸度半減期が70時間以上の場合:A
伸度半減期が60時間以上70時間未満の場合:B
伸度半減期が51時間以上60時間未満の場合:C
伸度半減期が51時間未満の場合:D
A、B、Cが良好であり、その中でもAが最も優れている。 Next, the film cut out in the same manner is treated with a pressure cooker manufactured by Tabai Espec Co., Ltd. under high-humidity heat conditions of a temperature of 125 ° C. and a relative humidity of 100% RH, and then the elongation at break is measured. In addition, it is set as n = 5 and it measures about each of the longitudinal direction of a film, and the width direction, and let the average value be the breaking elongation E1. Using the obtained breaking elongations E0 and E1, the elongation retention is calculated by the following equation (a). The treatment time is changed by one hour, and the treatment time at which the elongation retention is 50% or less is defined as the elongation half life.
(A) Elongation retention (%) = E1 / E0 × 100
From the obtained elongation half-life, the heat-and-moisture resistance of the film was determined as follows.
When elongation half-life is 70 hours or more: A
When the elongation half-life is 60 hours or more and less than 70 hours: B
When the elongation half-life is 51 hours or more and less than 60 hours: C
When elongation half-life is less than 51 hours: D
A, B, and C are good, and A is the best among them.
積層ポリエステルフィルムを1cm×20cmの大きさに、長辺がフィルムの長手方向・幅方向に平行となるようにそれぞれ切り出し、ASTM-D882(1997)に基づいて、チャック間5cm、引っ張り速度300mm/分にて引っ張ったときの破断強度を測定する。なお、サンプル数はn=5とし、また、フィルムの長手方向、幅方向のそれぞれについて測定した後、それらの平均値を求め、これをフィルムの破断強度S0とする。 F. Heat resistance of the laminated polyester film The laminated polyester film was cut into a size of 1 cm × 20 cm and the long sides were parallel to the longitudinal direction and the width direction of the film, respectively, and 5 cm between chucks based on ASTM-D882 (1997). The breaking strength when pulled at a pulling speed of 300 mm / min is measured. The number of samples is n = 5, and after measuring in the longitudinal direction and the width direction of the film, the average value thereof is obtained, and this is defined as the breaking strength S0 of the film.
(b) 強度保持率(%)=S1/S0×100
得られた伸度半減期から、フィルムの耐熱性を以下のように判定した。
強度半減期が60時間以上の場合:A
強度半減期が48時間以上60時間未満の場合:B
強度半減期が36時間以上48時間未満の場合:C
強度半減期が36時間未満の場合:D
A、B、Cが良好であり、その中でもAが最も優れている。 Next, the film cut in the same manner is subjected to a dry heat treatment under a high temperature condition of 200 ° C. in a gear oven manufactured by Tabai Espec Co., Ltd., and then the breaking strength is measured. In addition, it is set as n = 5 and it measures about each of the longitudinal direction of a film, and the width direction, and let the average value be breaking strength S1. Using the obtained breaking strengths S0 and S1, the elongation retention is calculated by the following equation (b). The treatment time is changed by one hour, and the treatment time at which the strength retention is 50% or less is defined as the strength half life.
(B) Strength retention (%) = S1 / S0 × 100
From the obtained elongation half-life, the heat resistance of the film was determined as follows.
When the strength half-life is 60 hours or more: A
When the strength half-life is 48 hours or more and less than 60 hours: B
When the strength half-life is 36 hours or more and less than 48 hours: C
When the strength half-life is less than 36 hours: D
A, B, and C are good, and A is the best among them.
フィルム厚みは、ダイヤルゲージを用い、JIS K7130(1992年)A-2法に準じて、フィルムを10枚重ねた状態で任意の5ヶ所について厚さを測定した。その平均値を10で除してフィルム厚みとした。 G. Laminated polyester film thickness (μm)
The film thickness was measured at any five locations using a dial gauge according to JIS K7130 (1992) A-2 method with 10 films stacked. The average value was divided by 10 to obtain the film thickness.
フィルム断面を、フィルム幅方向に平行な方向に、かつ、フィルムの厚み方向に垂直な方向に、ミクロトームで切り出す。該断面を走査型電子顕微鏡で5000倍の倍率で観察し、積層各層の厚み比率を求める。求めた積層比率と上記したフィルム厚みから、各層の厚みを算出する。 H. Thickness (μm) of each layer of laminated polyester film
A film cross section is cut out with a microtome in a direction parallel to the film width direction and in a direction perpendicular to the film thickness direction. The cross section is observed with a scanning electron microscope at a magnification of 5000 times to determine the thickness ratio of each layer. The thickness of each layer is calculated from the obtained lamination ratio and the above-described film thickness.
JIS P-8115(1994)に基づき試験を行う。積層ポリエステルフィルムを、測定したい方向が長辺となるように5mm×100mmに切り出し、東洋精機(株)製耐折試験機を用い、張力9.8N/mm2、クランプのR0.38mm、耐折角度135°、回転速度175cpmにて試験を行う。積層ポリエステルフィルムの幅方向、長手方向それぞれにn=5で試験を行い、フィルムが破壊するまでの回数を計測する。それらの平均値Nから下記式(c)で耐折強さFEを算出し、折り曲げ性を評価する。
(c)FE=logN
FE<4.1:折り曲げ性不良 (表中poorと記載)
4.1≦FE≦4.5:折り曲げ性良好 (表中fineと記載)
4.5<FE:折り曲げ性不良 (表中poorと記載)
J.打ち抜き性
高分子計器(株)製試験片打抜機を用い、JIS K-6251に記載の5号型ダンベル形状に積層ポリエステルフィルムを打ち抜く。フィルムを1枚ずつ打ち抜き、10枚打ち抜いた際に端面の割れ、剥がれが起きている枚数Mを数え、打ち抜き性を評価する。
0≦M≦2:打ち抜き性A
3≦M≦5:打ち抜き性B
6≦N≦10:打ち抜き性C
Aが最も優れ、Cが最も劣っている。 I. Bendability The test is performed based on JIS P-8115 (1994). Cut out the laminated polyester film to 5 mm x 100 mm so that the direction to be measured is the long side, and using a folding tester manufactured by Toyo Seiki Co., Ltd., tension 9.8 N / mm 2 , clamp R0.38 mm, folding resistance The test is performed at an angle of 135 ° and a rotation speed of 175 cpm. The test is performed with n = 5 in each of the width direction and the longitudinal direction of the laminated polyester film, and the number of times until the film breaks is measured. The folding strength FE is calculated from the average value N by the following formula (c), and the bendability is evaluated.
(C) FE = logN
FE <4.1: Poor bendability (described as “poor” in the table)
4.1 ≦ FE ≦ 4.5: Good bendability (described as fine in the table)
4.5 <FE: Poor bending property (described as “poor” in the table)
J. et al. Punching property A laminated polyester film is punched into a No. 5 type dumbbell shape described in JIS K-6251 using a test piece punching machine manufactured by Kobunshi Keiki Co., Ltd. The number of sheets M in which the end face is cracked or peeled when punching 10 sheets one by one is counted, and the punchability is evaluated.
0 ≦ M ≦ 2: Punchability A
3 ≦ M ≦ 5: Punchability B
6 ≦ N ≦ 10: Punchability C
A is the best and C is the worst.
オルトクロロフェノール100mlにポリエステル組成物を溶解させ(溶液濃度C=1.2g/dl)、その溶液の25℃での粘度を、オストワルド粘度計を用いて測定する。また、同様に溶媒の粘度を測定する。得られた溶液粘度、溶媒粘度を用いて、下記(c)式により、[η](dl/g)を算出し、得られた値でもって固有粘度(IV)とする。
(c)ηsp/C=[η]+K[η]2・C
(ここで、ηsp=(溶液粘度(dl/g)/溶媒粘度(dl/g))―1、Kはハギンス定数(0.343とする)である。)。 K. Intrinsic viscosity IV
The polyester composition is dissolved in 100 ml of orthochlorophenol (solution concentration C = 1.2 g / dl), and the viscosity of the solution at 25 ° C. is measured using an Ostwald viscometer. Similarly, the viscosity of the solvent is measured. Using the obtained solution viscosity and solvent viscosity, [η] (dl / g) is calculated by the following equation (c), and the obtained value is used as the intrinsic viscosity (IV).
(C) ηsp / C = [η] + K [η] 2 · C
(Where ηsp = (solution viscosity (dl / g) / solvent viscosity (dl / g)) − 1, K is a Huggins constant (assuming 0.343)).
表層を構成する樹脂として、PEN-A95質量部、PET-A5質量部をブレンドし、160℃で2時間真空乾燥した後押出機1に投入した。また、表層に接する層を構成する樹脂としてPET-A100質量部を160℃で2時間真空乾燥した後、押出機2に投入した。押出機内でそれぞれの原料を溶融させ、合流装置で押出機1に投入した樹脂がフィルムの両表層となるように合流させ、キャスティングドラム状に押し出し、3層構造をもつ積層シートを作製した。続いて該シートを加熱したロール群で予熱した後、95℃の温度で長手方向(MD方向)に3.3倍延伸を行った後、25℃の温度のロール群で冷却して一軸延伸フィルムを得た。得られた一軸延伸フィルムの両端をクリップで把持しながらテンター内の110℃の温度の加熱ゾーンで長手方向に直角な幅方向(TD方向)に3.7倍延伸した。さらに引き続いて、テンター内の熱処理ゾーンで220℃の温度で10秒間の熱処理を施し、さらに220℃の温度で4%幅方向に弛緩処理を行った。次いで、冷却ゾーンで均一に徐冷後、巻き取って、厚さ125μmの積層ポリエステルフィルムを得た。得られたフィルムの各特性を表に示す。耐熱性、耐湿熱性、加工性に優れたフィルムであることが分かった。 Example 1
As a resin constituting the surface layer, 95 parts by mass of PEN-A and 5 parts by mass of PET-A were blended, vacuum-dried at 160 ° C. for 2 hours, and then charged into the extruder 1. Further, 100 parts by mass of PET-A as a resin constituting a layer in contact with the surface layer was vacuum-dried at 160 ° C. for 2 hours, and then charged into the extruder 2. Each raw material was melted in an extruder, and the resin charged into the extruder 1 was merged by a merger so as to be both surface layers of the film, and extruded into a casting drum shape to produce a laminated sheet having a three-layer structure. Subsequently, the sheet is preheated with a heated roll group, then stretched 3.3 times in the longitudinal direction (MD direction) at a temperature of 95 ° C., and then cooled with a roll group at a temperature of 25 ° C. to be a uniaxially stretched film. Got. The obtained uniaxially stretched film was stretched 3.7 times in the width direction (TD direction) perpendicular to the longitudinal direction in a heating zone at a temperature of 110 ° C. in the tenter while holding both ends with clips. Subsequently, a heat treatment was performed for 10 seconds at a temperature of 220 ° C. in a heat treatment zone in the tenter, and a relaxation treatment was further performed in the 4% width direction at a temperature of 220 ° C. Next, the film was gradually cooled in a cooling zone and wound up to obtain a laminated polyester film having a thickness of 125 μm. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
表層を構成する樹脂に用いるPEN-AとPET-Aの混合比率、および積層ポリエステルフィルムの厚み、各層の厚みを表に記載の通りに変えた以外は、実施例1と同様にして積層ポリエステルフィルムを得た。得られたフィルムの各特性を表に示す。耐熱性、耐湿熱性、加工性に優れたフィルムであることが分かった。 (Examples 2 to 4, 9 to 16, 25, 26)
A laminated polyester film in the same manner as in Example 1 except that the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer, the thickness of the laminated polyester film, and the thickness of each layer were changed as described in the table. Got. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
表層を構成する樹脂に用いるPEN-AとPET-Aの混合比率、および積層ポリエステルフィルムの延伸工程を表に記載の通りに変えた以外は、実施例1と同様にして積層ポリエステルフィルムを得た。得られたフィルムの各特性を表に示す。延伸倍率を上げることによってR1、R2がより好ましい範囲となり、耐熱性、耐湿熱性に優れたフィルムが得られた。 (Examples 5 to 8)
A laminated polyester film was obtained in the same manner as in Example 1 except that the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer and the stretching process of the laminated polyester film were changed as described in the table. . Each characteristic of the obtained film is shown in the table. By increasing the draw ratio, R1 and R2 became more preferable ranges, and a film excellent in heat resistance and moist heat resistance was obtained.
実施例17は、フィルムの積層構成を2層とし、積層ポリエステルフィルムの各層の厚みを表に記載の通りに変えた以外は、実施例1と同様にして積層ポリエステルフィルムを得た。また、実施例18~20は、A層を構成する樹脂を表に記載のとおりに変えた以外は、実施例17と同様にして積層ポリエステルフィルムを得た。得られたフィルムの各特性を表に示す。耐熱性、耐湿熱性、加工性に優れたフィルムであることが分かった。 (Examples 17 to 20)
In Example 17, a laminated polyester film was obtained in the same manner as in Example 1, except that the laminated structure of the film was two layers and the thickness of each layer of the laminated polyester film was changed as described in the table. In Examples 18 to 20, laminated polyester films were obtained in the same manner as in Example 17 except that the resin constituting the A layer was changed as described in the table. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
表層の厚み、および積層ポリエステルフィルムの厚みを変えた以外は、実施例1と同様にして積層ポリエステルフィルムを得た。得られたフィルムの各特性を表に示す。耐熱性、耐湿熱性、加工性に優れたフィルムであることが分かった。 (Examples 21 to 24)
A laminated polyester film was obtained in the same manner as in Example 1 except that the thickness of the surface layer and the thickness of the laminated polyester film were changed. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
B層に用いる原料をPET/I-Aとし、延伸条件を表に記載の通りに変えた以外は、実施例4と同様にして積層ポリエステルフィルムを得た。得られたフィルムの各特性を表に示す。耐熱性、耐湿熱性、加工性に優れたフィルムであることが分かった。 (Examples 27 and 28)
A laminated polyester film was obtained in the same manner as in Example 4 except that the raw material used for the B layer was PET / IA and the stretching conditions were changed as shown in the table. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
B層に用いる原料をPET-Bとした以外は、実施例4と同様にして積層ポリエステルフィルムを得た。得られたフィルムの各特性を表に示す。耐熱性、耐湿熱性、加工性に優れたフィルムであることが分かった。 (Example 29)
A laminated polyester film was obtained in the same manner as in Example 4 except that the raw material used for the B layer was PET-B. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
表層を構成する樹脂に用いるPEN-AとPET-Aの混合比率、および積層ポリエステルフィルムの厚み、各層の厚み、および積層ポリエステルフィルムの延伸工程を表に記載の通りに変えた以外は、実施例1と同様にして積層ポリエステルフィルムを得た。得られた積層ポリエステルフィルムの各特性を表に示す。比較例1では表層を構成する樹脂がPENのみであるため、延伸により配向がつきにくく、R1,R2の値が(i)(ii)を満たさず、耐熱性、耐湿熱性、加工性に劣る。また、比較例2では、表層を構成する樹脂がPENのみであるため延伸性が悪く、高倍率延伸とすると製膜中に破れが多発し、フィルムを得ることができなかった。 (Comparative Examples 1 to 4, 7 to 12)
Example except that the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer, the thickness of the laminated polyester film, the thickness of each layer, and the stretching process of the laminated polyester film were changed as described in the table 1 to obtain a laminated polyester film. Each characteristic of the obtained laminated polyester film is shown in the table. In Comparative Example 1, since the resin constituting the surface layer is only PEN, orientation is not easily achieved by stretching, and the values of R1 and R2 do not satisfy (i) and (ii), and the heat resistance, moist heat resistance, and workability are poor. In Comparative Example 2, the resin constituting the surface layer was only PEN, so that the stretchability was poor. When high-strength stretching was used, tearing occurred frequently during film formation, and a film could not be obtained.
表層を構成する樹脂に用いる原料を、PET/N-A、PET/N-Bとした以外は、実施例1と同様にして積層ポリエステルフィルムを得た。積層ポリエステルフィルムの各特性を表に示す。共重合体を用いているため、延伸による配向を付与することが難しく、R1、R2の値が(i)(ii)を満たさず、また、表層を構成する樹脂の融点が260℃に満たないため耐熱性、耐湿熱性に劣ることが分かった。 (Comparative Examples 5 and 6)
A laminated polyester film was obtained in the same manner as in Example 1 except that the raw material used for the resin constituting the surface layer was PET / NA and PET / NB. Each characteristic of the laminated polyester film is shown in the table. Since a copolymer is used, it is difficult to impart orientation by stretching, the values of R1 and R2 do not satisfy (i) and (ii), and the melting point of the resin constituting the surface layer is less than 260 ° C. Therefore, it turned out that it is inferior to heat resistance and heat-and-moisture resistance.
表層を構成する樹脂の押出温度を300℃とし、表層を構成する樹脂に用いるPEN-AとPET-Aの混合比率、および積層ポリエステルフィルムの厚み、各層の厚み、および積層ポリエステルフィルムの延伸工程を表に記載の通りとした以外は、実施例1と同様にして積層ポリエステルフィルムを得た。表層を構成する樹脂の押出温度が高く、表層を構成する樹脂同士のエステル交換により共重合化が進み、延伸による配向を付与することが難しく、R1、R2の値が(i)(ii)を満たさず、また、表層を構成する樹脂の融点が260℃に満たないため耐熱性、耐湿熱性に劣ることが分かった。 (Comparative Examples 13 and 14)
The extrusion temperature of the resin constituting the surface layer is 300 ° C., the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer, the thickness of the laminated polyester film, the thickness of each layer, and the stretching process of the laminated polyester film A laminated polyester film was obtained in the same manner as in Example 1 except that it was as described in the table. The extrusion temperature of the resin constituting the surface layer is high, the copolymerization proceeds by transesterification of the resins constituting the surface layer, it is difficult to impart orientation by stretching, and the values of R1 and R2 are (i) (ii) It did not satisfy | fill, and since melting | fusing point of resin which comprises a surface layer was less than 260 degreeC, it turned out that it is inferior to heat resistance and heat-and-moisture resistance.
表層を構成する樹脂に用いるPEN-AとPET-Aの混合比率、および積層ポリエステルフィルムの厚み、各層の厚み、および積層ポリエステルフィルムの延伸工程を表に記載の通りに変えた以外は、実施例1と同様にして積層ポリエステルフィルムを得た。得られた積層ポリエステルフィルムの各特性を表に示す。フィルムの厚みが120μm以下であるものの、B層に対するA層の厚みの比率を低くすることで、A層を構成する樹脂の配向がつきやすく、耐湿熱性、耐熱性に優れることがわかった。一方で、フィルム厚みが薄いため実施例1に比べて加工性(打ちぬき性)にやや劣るものの、問題ないレベルであった。 (Examples 30 to 36)
Example except that the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer, the thickness of the laminated polyester film, the thickness of each layer, and the stretching process of the laminated polyester film were changed as described in the table 1 to obtain a laminated polyester film. Each characteristic of the obtained laminated polyester film is shown in the table. Although the thickness of the film was 120 μm or less, it was found that by reducing the ratio of the thickness of the A layer to the B layer, the resin constituting the A layer was easily oriented, and the heat and heat resistance and heat resistance were excellent. On the other hand, although the film thickness was thin, the workability (punchability) was slightly inferior to that of Example 1, but the level was satisfactory.
実施例35の積層ポリエステルフィルムを用いて、実施例35のA層が最表層となるように、東レ(株)製トレリナ(登録商標)3000を、B層側に、接着剤層を介して貼り合わせた。構成は、実施例35のフィルム/接着剤層/トレリナとした。接着剤層は、東レファインケミカル製エポキシ系接着剤ケミットTE2301を乾燥後の厚みで3μmとなるようにグラビアコーターで調整した。東レ(株)製トレリナの厚みは、実施例37では100μm、実施例38では15μmのものを用いた。得られたフィルムの特性を表に示す。耐熱性、耐湿熱性、加工性に優れることがわかった。 (Examples 37 and 38)
Using the laminated polyester film of Example 35, paste Torayna (registered trademark) 3000 manufactured by Toray Industries, Inc. on the B layer side with an adhesive layer so that the A layer of Example 35 is the outermost layer. Combined. The configuration was the film / adhesive layer / tolerina of Example 35. The adhesive layer was adjusted with a gravure coater so that the thickness after drying epoxy adhesive chemit TE2301 manufactured by Toray Fine Chemical was 3 μm. The thickness of Toray Industries, Inc.'s Torelina was 100 μm in Example 37 and 15 μm in Example 38. The properties of the obtained film are shown in the table. It was found to be excellent in heat resistance, moist heat resistance and processability.
実施例35のフィルムを用いて、実施例35のA層が最表層となるように、東レ(株)製トレリナ(登録商標)3000(厚み100μm)の両面に、接着剤層を介して貼り合わせた。構成は、実施例35のフィルム/接着剤層/トレリナ/接着剤層/実施例35のフィルムとした。得られたフィルムの特性を表に示す。耐熱性、耐湿熱性、加工性に優れることがわかった。 (Example 39)
Using the film of Example 35, both layers of Torayna (registered trademark) 3000 (thickness 100 μm) manufactured by Toray Industries, Inc. are bonded via an adhesive layer so that layer A of Example 35 is the outermost layer. It was. The configuration was the film of Example 35 / adhesive layer / tolerina / adhesive layer / film of Example 35. The properties of the obtained film are shown in the table. It was found to be excellent in heat resistance, moist heat resistance and processability.
フィルム長手方向に一軸延伸した後、易滑性を付与する目的でバーコートを用いて、フィルムの片側表面に、塗布厚み約8μmで下記の塗剤を塗布した以外は、実施例1と同様にして積層ポリエステルフィルムを得た。塗剤としては、塗液としては水を用い、DIC(株)製バーノック(登録商標)310Eを100重量部に対し、日産化学工業(株)製コロイダルシリカスノーテックス(登録商標)ST-50を5重量部の濃度となるように調整し、固形分重量として5重量%としたものを用いた。得られたフィルムの特性を表に示す。実施例1と同様、耐熱性、耐湿熱性、加工性に優れることがわかった。 (Example 40)
After uniaxially stretching in the longitudinal direction of the film, the same coating as in Example 1 was applied except that the following coating agent was applied to one surface of the film with a coating thickness of about 8 μm using a bar coat for the purpose of imparting easy slipperiness. Thus, a laminated polyester film was obtained. As a coating agent, water is used as a coating liquid, and 100 parts by weight of Bernock (registered trademark) 310E manufactured by DIC Corporation is used. Colloidal silica snowtex (registered trademark) ST-50 manufactured by Nissan Chemical Industries, Ltd. is used. The concentration was adjusted to 5 parts by weight, and the solid content weight was 5% by weight. The properties of the obtained film are shown in the table. As in Example 1, it was found that heat resistance, heat and humidity resistance, and workability were excellent.
表層を構成する樹脂としてPEN-BおよびPET-Cを用い、表層に接する層を構成する樹脂としてPET-Cを用いた以外は、実施例1と同様にして積層ポリエステルフィルムを得た。得られたフィルムの各特性を表に示す。耐熱性、耐湿熱性、加工性に優れたフィルムであることが分かった。PEN-Aに代えてPEN-B、PET-Aに代えてPET-Cを用いたため、耐湿熱性に優れることがわかる。 (Example 41)
A laminated polyester film was obtained in the same manner as in Example 1 except that PEN-B and PET-C were used as the resin constituting the surface layer, and PET-C was used as the resin constituting the layer in contact with the surface layer. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability. Since PEN-B is used in place of PEN-A and PET-C is used in place of PET-A, it can be seen that the heat and heat resistance is excellent.
表層を構成する樹脂としてPEN-AおよびPET-Dを用い、表層に接する層を構成する樹脂としてPET-Aを用いた以外は、実施例1と同様にして積層ポリエステルフィルムを得た。得られたフィルムの各特性を表に示す。耐熱性、耐湿熱性、加工性に優れたフィルムであることが分かった。 (Example 42)
A laminated polyester film was obtained in the same manner as in Example 1 except that PEN-A and PET-D were used as the resin constituting the surface layer, and PET-A was used as the resin constituting the layer in contact with the surface layer. Each characteristic of the obtained film is shown in the table. It was found that the film was excellent in heat resistance, moist heat resistance and processability.
表層を構成する樹脂に用いるPEN-AとPET-Aの混合比率、および積層ポリエステルフィルムの厚み、各層の厚み、および積層ポリエステルフィルムの延伸工程を表に記載の通りに変えた以外は、実施例1と同様にして積層ポリエステルフィルムを得た。得られた積層ポリエステルフィルムの各特性を表に示す。延伸時の面積倍率が17倍を超えるため、表層を構成する樹脂の分子鎖が規則正しく配列し、結晶部分が多くなるためR1,R2の値が(i)(ii)を満たさず、加工性に劣る。 (Comparative Example 15)
Example except that the mixing ratio of PEN-A and PET-A used for the resin constituting the surface layer, the thickness of the laminated polyester film, the thickness of each layer, and the stretching process of the laminated polyester film were changed as described in the table 1 to obtain a laminated polyester film. Each characteristic of the obtained laminated polyester film is shown in the table. Since the area ratio at the time of stretching exceeds 17 times, the molecular chains of the resin constituting the surface layer are regularly arranged, and the number of crystal parts increases, so the values of R1 and R2 do not satisfy (i) (ii) and workability is improved. Inferior.
Claims (9)
- 以下(1)~(3)を満たす、少なくとも2層からなる積層ポリエステルフィルム。
(1)少なくとも一方の表面が、フーリエ変換型赤外分光法(FT-IR)にて測定したとき、1452cm-1に観察されるスペクトル強度r1と、1332cm-1に観察されるスペクトル強度r2と、1602cm-1に観察されるスペクトル強度rから求められるR1、R2が以下の関係を満たすこと。
(i)0.2≦R1≦0.4
(ii)1.25≦R2≦1.50
ここで、R1=r1/r、R2=r2/r
(2)(1)を満たす表面が、フーリエ変換型赤外分光法(FT-IR)にて測定したとき、1018cm-1に観察されるスペクトル強度r3と、1602cm-1に観察されるスペクトル強度rから求められるR3が以下の関係を満たすこと。
(iii) 1.20≦R3≦2.00
ここで、R3=r3/r
(3)(1)(2)を満たす表面を有する層(該層をA層とする)を構成する樹脂の融点が260℃以上280℃以下であること。 A laminated polyester film comprising at least two layers satisfying the following (1) to (3).
(1) at least one surface, when measured by Fourier transform infrared spectroscopy (FT-IR), and the spectral intensity r1 observed in 1452Cm -1, the spectrum intensity r2 observed in 1332 cm -1 R1 and R2 obtained from the spectral intensity r observed at 1602 cm −1 satisfy the following relationship.
(I) 0.2 ≦ R1 ≦ 0.4
(Ii) 1.25 ≦ R2 ≦ 1.50
Here, R1 = r1 / r, R2 = r2 / r
(2) a surface that satisfies (1), when measured at a Fourier transform infrared spectroscopy (FT-IR), and the spectral intensity r3 observed in 1018 cm -1, the spectrum intensity observed in 1602 cm -1 R3 calculated from r satisfies the following relationship.
(Iii) 1.20 ≦ R3 ≦ 2.00
Where R3 = r3 / r
(3) The melting point of the resin constituting the layer having a surface satisfying (1) and (2) (this layer is referred to as layer A) is 260 ° C. or higher and 280 ° C. or lower. - 以下(4)を満たす、請求項1または2に記載の積層ポリエステルフィルム。
(4)フィルムの総厚みTが120μm以上500μm以下。 The laminated polyester film according to claim 1 or 2, which satisfies the following (4).
(4) The total thickness T of the film is 120 μm or more and 500 μm or less. - 上記A層を構成する樹脂のガラス転移温度(Tg1)℃と、上記A層に隣接する層(該層をB層とする)を構成する樹脂のガラス転移温度(Tg2)℃との差が以下の関係を満たす請求項1または2に記載の積層ポリエステルフィルム。
30℃≦Tg1-Tg2≦40℃ The difference between the glass transition temperature (Tg1) ° C. of the resin constituting the A layer and the glass transition temperature (Tg2) ° C. of the resin constituting the layer adjacent to the A layer (this layer is referred to as B layer) is as follows: The laminated polyester film according to claim 1 or 2, satisfying the relationship:
30 ° C ≦ Tg1-Tg2 ≦ 40 ° C - 上記B層が、フーリエ変換型赤外分光法(FT-IR)にて測定したとき、1388cm-1に観察されるスペクトル強度r4と1372cm-1に観察されるスペクトル強度r5から求められるR4が以下の関係を満たす請求項1から3のいずれかに記載の積層ポリエステルフィルム。
(iv)0.95≦R4≦1.05
ここで、R4=r4/r5 The B layer is, when measured by Fourier transform infrared spectroscopy (FT-IR), R4 is less obtained from the spectral intensity r5 observed in spectral intensity r4 and 1372cm -1 which is observed 1388Cm -1 The laminated polyester film according to any one of claims 1 to 3, which satisfies the above relationship.
(Iv) 0.95 ≦ R4 ≦ 1.05
Here, R4 = r4 / r5 - フィルムの両側の表層がA層からなる、少なくとも3層からなる請求項1から4のいずれかに記載の積層ポリエステルフィルム。 The laminated polyester film according to any one of claims 1 to 4, wherein the surface layers on both sides of the film are composed of A layers and are composed of at least three layers.
- 上記B層を構成する樹脂の融点が253℃以上258℃以下である請求項1から5のいずれかに記載の積層ポリエステルフィルム。 The laminated polyester film according to any one of claims 1 to 5, wherein the resin constituting the B layer has a melting point of 253 ° C or higher and 258 ° C or lower.
- 積層ポリエステルフィルムを構成するポリエステル樹脂の末端カルボキシル基量が15eq./t以下である請求項1から6のいずれかに記載の積層ポリエステルフィルム。 The amount of terminal carboxyl groups of the polyester resin constituting the laminated polyester film is 15 eq. The laminated polyester film according to any one of claims 1 to 6, which is / t or less.
- モーターの電気絶縁部材として用いられる請求項1から7のいずれかに記載の積層ポリエステルフィルム。 The laminated polyester film according to any one of claims 1 to 7, which is used as an electric insulating member of a motor.
- 請求項1から8のいずれかに記載の積層ポリエステルフィルムを含み、積層ポリエステルフィルムの(1)(2)を満たす表面を少なくとも片側の最表層に有する積層フィルム。
A laminated film comprising the laminated polyester film according to claim 1 and having a surface satisfying (1) and (2) of the laminated polyester film on at least one outermost layer.
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WO2023210443A1 (en) * | 2022-04-27 | 2023-11-02 | 東洋紡株式会社 | Poly(ethylene terephthalate)-based resin film, polarizing plate including same, transparent electroconductive film, touch panel, and image display device |
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WO2018066670A1 (en) * | 2016-10-05 | 2018-04-12 | 大日本印刷株式会社 | Packaging material for battery, manufacturing method therefor, and battery |
US20220024083A1 (en) * | 2018-12-21 | 2022-01-27 | Tata Steel Ijmuiden B.V. | Method for producing a polymer coated metal strip and polymer coated metal strip produced thereby |
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Also Published As
Publication number | Publication date |
---|---|
CN105451993B (en) | 2018-06-15 |
JPWO2015019885A1 (en) | 2017-03-02 |
CN105451993A (en) | 2016-03-30 |
TW201509671A (en) | 2015-03-16 |
JP6507640B2 (en) | 2019-05-08 |
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