CN104321372A - Polyester film and method for producing same - Google Patents
Polyester film and method for producing same Download PDFInfo
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- CN104321372A CN104321372A CN201380025562.5A CN201380025562A CN104321372A CN 104321372 A CN104321372 A CN 104321372A CN 201380025562 A CN201380025562 A CN 201380025562A CN 104321372 A CN104321372 A CN 104321372A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Provided is a polyester film which is industrially practicable, while having an excellent balance between the mechanical characteristics in the MD direction and the mechanical characteristics in the TD direction, excellent impact resistance and the like. This polyester film is formed of a polyester resin that contains 60% by mass or more of a polybutylene terephthalate, and has an elongation at break in the MD of 80% or more, an elongation at break in the TD of 80% or more, a plane orientation of 0.12-0.14, an impact strength of 0.05 J/mum or more and a puncture strength of 0.5 N/mum or more.
Description
Technical field
The present invention relates to polyester film and manufacture method thereof.More particularly, polyester film and the manufacture method thereof of that be applicable to the purposes of the film using nylon film or other softnesses at present, shock-resistance, bendability, mechanical strength harmony excellence is related to.
Background technology
Mechanical characteristic, the excellent impact resistance of polybutylene terephthalate (PBT), therefore use as engineering plastics so far, particularly, productivity fast from the viewpoint of crystallization velocity is excellent also as useful materials'use.But, PBT due to crystallization velocity fast, biaxial stretch-formed difficulty.This is because, the orientation of drawing process causes crystallization, cause the difficulty that stretches.Relative to this, in order to play the characteristic that PBT has originally, carry out utilizing biaxial stretch-formedization to improve planar orientation thus improve the research for the purpose of the mechanical characteristic, shock-resistance of film in the past since 40 years, but so far, commercially available PBT film is still the cast sheet do not stretched and the film utilizing inflation method to obtain, the orientation of the PBT of these films is insufficient, is therefore difficult to the characteristic having played PBT originally.Particularly for the PBT film utilizing inflation method to obtain, because its manufacture method causes stretching ratio to be difficult to evenly, there is the problem that thickness and precision is not good, and then cannot uprise due to planar orientation coefficient, also exist and pierce through the problems such as intensity is low.Therefore, the PBT film that the biaxial stretching process utilizing tenter machine to carry out obtains is studied.Below, some discussion are carried out in the research for the PBT film in past.
At present, there will be a known following technology: be after the mode of less than 3.5 times stretches on TD direction to make stretching ratio, stretch in the MD direction with the Deformation velocity of more than 100000%/min and manufacture biaxial stretch-formed PBT film, thus manufacture the technology (for example, see patent documentation 1) of the film without uneven thickness of Uniform Tension.But known there are the following problems from the result of embodiment for described prior art: owing to only accelerating the Deformation velocity in MD direction, elongation can be low, cannot become and obtain balanced film in MD direction and TD direction.
In addition, there will be a known following technology: based on experimental result, draft temperature is calculated by degree of crystallinity when not stretching, implement the stretching in MD (or TD) direction with low range more than this temperature after, at high temperature stretch in the direction orthogonal with the draw direction of first stage, the film (for example, see patent documentation 2) of the excellent impact resistance be inhibited that ruptures when manufacturing uneven thickness, masking thus.But, for described prior art, be stretched as the Tg's (45 DEG C) of 120 DEG C and PBT from the viewpoint of subordinate phase, it is stretching at higher temperatures, be that the state that oriented crystalline has been carried out can carry out the such stretching of reorientation in the direction of subordinate phase, therefore there is the problem that the harmony of the mechanical characteristic in MD direction and TD direction is not good.
There will be a known following technology: by being undertaken alternately laminated by the resin beyond PBT and the PBT such as polyethylene terephthalate (PET), PEN (PEN), manufacture the film (for example, see patent documentation 3) of gas barrier property, pinhole resistance excellence thus.But the layer of PET, PEN resin formation beyond the stacked PBT of described prior art, therefore becomes the stretching of draft temperature under the draft temperature of Tg higher than PET, PEN of PBT, from the Tg of PBT, is stretching at high temperature.Therefore, do not play the feature of PBT film originally, and the resin in film consists of two kinds, be therefore difficult to cutting during masking to consider to be worth doing to wait again to add in raw material recycle, there is the disadvantageous problem of economic aspect.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 51-146572 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 51-40904 publication
Patent documentation 3: Japanese Patent No. 4273855 publication
Summary of the invention
the problem that invention will solve
The present invention completes for background with the problem of described prior art.Namely, the object of the invention is to: the fracture caused when stretching in order to the PBT suppressing crystallization velocity fast, particularly by suppress the molten resin that width is discharged from mould velocity of shear, cast time speed of cooling difference caused by degree of crystallinity uneven, reduce the difference in specific gravity in the direction of the width of the unstretched state of film, there is provided thus and significantly suppress fracture, can industrially implement, the harmony, shock-resistance etc. of the mechanical characteristic in MD/TD direction improve excellent polyester film and manufacture method thereof.
for the scheme of dealing with problems
The present inventor etc. in order to achieve the above object, conduct in-depth research, and result completes the present invention.
Namely, the present invention is a kind of polyester film, it is formed by the vibrin comprising the above PBT of 60 quality %, and the elongation at break of MD is more than 80%, the elongation at break of TD is more than 80%, planar orientation is 0.12 ~ 0.14, shock strength is more than 0.05J/ μm and to pierce through intensity be more than 0.5N/ μm.
the effect of invention
According to the present invention, in polyester film and manufacture method thereof, in order to the fracture that the PBT suppressing crystallization velocity fast causes when stretching, particularly uneven by the velocity of shear of molten resin that suppresses to discharge from mould at width, degree of crystallinity that the difference of the speed of cooling of Jiao Zhu Time causes, reduce the difference in specific gravity in the direction of the width of film unstretched state, significantly suppress fracture during film stretching thus, industrially can implement, and the harmony, shock-resistance etc. of the mechanical characteristic in MD and TD direction can be improved.
Embodiment
Below, the present invention will be described in detail.
The vibrin that the present invention uses is using PBT as main composition composition, and the containing ratio of PBT is preferably more than 60 quality %, more preferably more than 70 quality %, is particularly preferably more than 75 quality %, most preferably is more than 80 quality %.During lower than 60 quality %, the shock strength of film and pinhole resistance reduce, and film characteristics is also insufficient.
For the PBT used as main composition composition, as dicarboxylic acid component, terephthalic acid is more than 90 % by mole is preferred, is more preferably more than 95 % by mole, more preferably more than 98 % by mole, most preferably is 100 % by mole.As glycol component, BDO is more than 90 % by mole is preferred, the material beyond the by product be more preferably more than 95 % by mole, more preferably more than 97 % by mole, being generated when most preferably not comprising polymerization by the ehter bond of BDO.
As can the dicarboxylic acid component of copolymerization, can enumerate: m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, diphenyl dicarboxylic acid, cyclohexane dicarboxylic acid, hexanodioic acid, nonane diacid, sebacic acid etc.As can the glycol component of copolymerization, can enumerate: ethylene glycol, 1,3-PD, 1,2-PD, neopentyl glycol, 1,5-pentanediol, 1,6-hexylene glycol, Diethylene Glycol, cyclohexanediol, polyoxyethylene glycol, polytetramethylene glycol, polycarbonate diol etc.
These need can meet and aftermentioned other vibrin, additive amount between harmony and film shock strength, pierce through the scope of intensity, adjust the copolymerization amount of each monomer.
In addition, constituent as other has no particular limits, can add in described vibrin polyethylene terephthalate (PET), PEN (PEN), PBN (PBN), Poly(Trimethylene Terephthalate) (PPT) etc., other vibrin, as additive, for improving bending time pinhole resistance and the Polyester that makes any person's copolymerization in soft polyether components, polycarbonate component, polyester component and obtain and polyamide-based elastomerics.
The lower limit of the addition of these additives is preferably 0 quality %, and the upper limit is preferably 20 quality %.During more than 20%, above-mentioned effect is saturated, in addition, can cause the transparency reduction etc. of film.
The lower limit of resin melt temperature is preferably 200 DEG C, and during lower than 200 DEG C, the discharge of molten resin can become unstable.The upper limit of resin melt temperature is preferably 320 DEG C, during more than 320 DEG C, can cause the deterioration of resin.
Previous polyesters resin can contain current known additive, such as lubricant, stablizer, tinting material, antioxidant, static inhibitor, UV light absorber etc. as required.
As lubricant kind, the inorganic system lubricants such as preferred organic base lubricant, silicon-dioxide, calcium carbonate, aluminum oxide, more preferably silicon-dioxide, calcium carbonate, particularly preferably calcium carbonate.Thus, the transparency and the sliding of film can be embodied.
The lower limit of lubricant concentration is preferably 100ppm, and during lower than 100ppm, the sliding of film can reduce.The upper limit of lubricant concentration is preferably 20000ppm, and during more than 20000ppm, the transparency of film can reduce.
As the key for obtaining film of the present invention, need the difference of the degree of crystallinity of the width reducing the non-stretched film when casting.Therefore, as concrete method, the cooling roller can enumerated to low temperature is cast.In addition, in order to cool the face do not contacted with cooling roller, touch roll also can be set to improve cooling efficiency.
In addition, as other method, the discoveries such as the present inventor: poor by using novel method described later can reduce the degree of crystallinity of the width of non-stretched film.That is, found that can reduce the difference of the degree of crystallinity of the width of non-stretched film, tensile stress when TD can be made to stretch is evenly distributed when casting by the raw material multiple stratification of same composition being cast again.At present, when casting, the degree of crystallinity of the end of non-stretched film uprises, and the degree of crystallinity step-down of the central part of non-stretched film, when therefore stretching in TD direction, tensile stress becomes uneven on the width of non-stretched film, thus film easily ruptures, therefore, need to carry out TD stretching at higher temperatures.Although in contrast, this reason infers, even if also there is the interface of layer when same resin is stacked, because this interface causes crystallization to accelerate, on the other hand, can think that the large crystallization exceeding layer is suppressed, therefore become even in the degree of crystallinity of the width of non-stretched film.As concrete method, common multiple stratification device (multilayer is for stub bar, static mixer, multilayer branch manifold etc.) can be used, such as, use the forcing machine of more than two thermoplastic resin sent from various flows road to be used the method etc. being laminated for multilayer for stub bar, static mixer, multi-manifold etc.It should be noted that, when the raw material multiple stratification by same composition, only can use a forcing machine, above-mentioned multiple stratification device is imported to the melting pipeline (melt line) between forcing machine to mould, reach object of the present invention thus.
It should be noted that, the raw material of same composition refers to, when the forcing machine of use more than two, set in the content of each raw material compounding from the thermoplastic resin that each forcing machine is sent, the difference of biggest quality % and minimum mass % allow be below 10 quality %, be further below 5 quality %, be in particular below 2 quality %.When polyester uses multipolymer, set in the content of the monomer of copolymerization compounding the thermoplastic resin sent from each forcing machine, maximum % by mole allow to be less than 5 % by mole with the difference of minimum % by mole, be further less than 3 % by mole, be in particular less than 2 % by mole.In addition, the molecular weight of each raw material also can be different, but when trying to achieve the weight-average molecular weight of vinylbenzene conversion by GPC, with the difference of its molecular weight be preferably less than 30% divided by the value of the molecular weight of the large material of molecular weight, more preferably less than 20%, be particularly preferably less than 10%, as long as in this scope, even if the molecular weight of each raw material is different, also allow as each identical raw material.
It should be noted that, only use a forcing machine that above-mentioned multiple stratification device is imported the method for the melting pipeline between forcing machine to mould, consider it is also preferred method from the management aspect of the simplicity of device, each raw material.
The lower limit of die temperature is preferably 200 DEG C, and during lower than 200 DEG C, the discharge of molten resin is unstable, and the thickness of film can become uneven.The upper limit of die temperature is preferably 350 DEG C, during more than 350 DEG C, except the thickness of film become uneven except, also can cause the deterioration of resin, cause bad order because of die lip pollution etc.
The lower limit of chill-roll temperature is preferably-10 DEG C, and during lower than-10 DEG C, the uniformization effect of the degree of crystallinity of the width of non-stretched film is saturated.The upper limit of chill-roll temperature is preferably 80 DEG C, and during more than 80 DEG C, the degree of crystallinity of non-stretched film becomes too high thus stretches and becomes difficulty.In order to reduce the difference of the degree of crystallinity of the width of non-stretched film, it is effective for reducing degree of crystallinity, and from this viewpoint, when not using the method for multiple stratification described later etc., chill-roll temperature is preferably less than 10 DEG C, is less than 5 DEG C further.Now, in order to prevent condensation, preferably reduce the ambient moisture near cooling roller.On the other hand, can be poor by using the methods such as multiple stratification described later to reduce the degree of crystallinity of the width of non-stretched film, now, even if also can cast at the temperature of 15 ~ 40 DEG C.
The temperature head of the width of cooling roller is less is good, and preferable temperature difference is less than 5 DEG C, more preferably less than 3 DEG C.When temperature head is more than 5 DEG C, sometimes cannot reduce the difference of the degree of crystallinity of the width of the non-stretched film when casting.
When casting, the temperature on cooling roller surface is caused to rise due to the resin of surface contact high temperature.Usually, cooling roller in inside by pipe arrangement circulation water coolant thus cool, but need to guarantee sufficient cooling water inflow, design pipe arrangement configuration, carry out keeping in repair to make not adhere to the temperature head that mud etc. reduces the width on cooling roller surface on pipe arrangement.Should be noted that when particularly cooling at low temperatures not using the method for multiple stratification etc.
During the casting of multilayered structure, be at least more than 3 layers, be preferably more than 5 layers, be more preferably more than 8 layers, most preferably be more than 100 layers.When the number of plies is few, the difference in specific gravity of the width of non-stretched film becomes large, and the improvement effect of stretchiness is little.When for more than 100 layers, reduce the effect stability of the difference in specific gravity of the width of non-stretched film, in addition, the thickness evenness of each layer is also stablized, and also has the effects such as appearance investigation, therefore preferably.
Then drawing process is described.For drawing process, biaxial stretch-formed the while of can being also can be biaxial stretch-formed successively, but in order to improve the intensity that pierces through of film, need the planar orientation coefficient improving film, is preferably biaxial stretch-formed successively from this viewpoint.
The lower limit of MD draft temperature is preferably 40 DEG C, is more preferably 45 DEG C.During lower than 40 DEG C, easily cause fracture.The upper limit of MD draft temperature is preferably 100 DEG C, is more preferably 95 DEG C.During more than 100 DEG C, the mechanical characteristic of film is sometimes caused to reduce because being difficult to orientation.
The lower limit of MD stretching ratio is preferably 2.5 times, lower than 2.5 time, sometimes cause the mechanical characteristic of film, uneven thickness to worsen because being difficult to orientation.The upper limit of MD stretching ratio is preferably 5 times, during more than 5 times, improves the mechanical strength of film, the effect of uneven thickness can be saturated.
The lower limit of TD draft temperature is preferably 40 DEG C, during lower than 40 DEG C, easily causes the fracture of film.The upper limit of TD draft temperature is preferably 100 DEG C, during more than 100 DEG C, sometimes causes the mechanical characteristic of film to reduce because being difficult to orientation.
The lower limit of TD stretching ratio is preferably 2.5 times, during lower than 2.5 times, sometimes causes mechanical characteristic, uneven thickness to worsen because being difficult to orientation.The upper limit of TD stretching ratio is preferably 5 times, during more than 5 times, improves the mechanical strength of film, the effect of uneven thickness can be saturated.
The lower limit of TD heat fixation temperature is preferably 150 DEG C, and during lower than 150 DEG C, the percent thermal shrinkage of film becomes large, cause add man-hour skew, contraction.The upper limit of TD heat fixation temperature is preferably 250 DEG C, and during more than 250 DEG C, thin film melt, in addition, even if non-melting also can become fragile.
The lower limit of TD relaxation rate is preferably 0.5%, lower than 0.5% time, easily cause the fracture of film when heat fixation.The upper limit of TD relaxation rate is preferably 10%, and during more than 10%, film produces lax grade thus generation uneven thickness.
For of the present invention biaxial stretch-formed after film, the lower limit of film thickness is preferably 3 μm, is more preferably 5 μm, more preferably 8 μm.During lower than 3 μm, can be not enough as thin film strength.The upper limit of film thickness is preferably 100 μm, is more preferably 75 μm, more preferably 50 μm.During more than 100 μm, film becomes blocked up and causes the processing in object of the present invention to become difficulty.
About the uneven thickness in roller total width, the maximum ga(u)ge in total width and the difference of minimum thickness relative to mean thickness be preferably in 0 ~ 25% scope, be more preferably in 0 ~ 20% scope.During more than 25%, the distortion etc. caused when can produce roller bad order, secondary processing, thus not preferred.In order to reduce the difference of maximum ga(u)ge in total width and minimum thickness, needing the stretching ratio making width even, therefore, needing to make degree of crystallinity when not stretching even in advance.
The lower limit of the proportion of the central part of non-stretched film of the present invention is preferably 1.25g/cm
3, lower than 1.25g/cm
3time, the effect improving the stretchiness of non-stretched film can be saturated.The upper limit of the proportion of central part is preferably 1.3g/cm
3, more than 1.3g/cm
3time, degree of crystallinity becomes too high thus causes the difficulty that stretches.
The upper limit of the difference of the width proportion of non-stretched film of the present invention is preferably 0.03g/cm
3, more than 0.03g/cm
3time, the tensile stress of width is uneven, thus causes the fracture of film, causes the stretching of the width of film uneven, becomes the reason of uneven thickness, physical property inequality.
The lower limit of the MD Young's modulus of film of the present invention is preferably 1GPa, and during lower than 1GPa, film easily extends, and adds spacing (pitch) can be caused man-hour to offset at printing, lamination etc.The upper limit of MD Young's modulus is preferably 2GPa, and during more than 2GPa, after the laminating such as film and various sealing agents, it is unfavorable to have in the processibilities such as drawing processing.
The lower limit of the TD Young's modulus of film of the present invention is preferably 1GPa, and during lower than 1GPa, film easily extends, and can cause problem man-hour adding.The upper limit of TD Young's modulus is preferably 2GPa, and during more than 2GPa, after the laminating such as film and various sealing agents, it is unfavorable to have in the processibilities such as drawing processing.It should be noted that, TD Young's modulus can be located in scope by heat fixation temperature.
The lower limit of the TD breaking tenacity of film of the present invention is preferably 100MPa, and during lower than 100MPa, the man-hour that adds of film can cause fracture etc.The upper limit of TD breaking tenacity is preferably 500MPa, and during more than 500MPa, the effect improving the breaking tenacity of film can be saturated.
The lower limit of the MD elongation at break of film of the present invention is preferably 80%, is more preferably 90%.Lower than 80% time, film and various sealing agents etc. laminating after, it is unfavorable to have in the processibilities such as drawing processing.The upper limit of MD elongation at break has no particular limits, and is preferably 200%.MD elongation at break can be located in scope by MD multiplying power, heat fixation temperature.
The lower limit of the TD elongation at break of film of the present invention is preferably 80%, is more preferably 90%.Lower than 80% time, film and various sealing agents etc. laminating after, it is unfavorable to have in the processibilities such as drawing processing.The upper limit of TD elongation at break has no particular limits, and is preferably 500%.TD elongation at break can be located in scope by TD multiplying power, heat fixation temperature.
The lower limit of the planar orientation coefficient of film of the present invention is preferably 0.12, lower than 0.12 time, piercing through intensity, shock strength etc. can reduce.The upper limit of planar orientation coefficient is preferably 0.14, and during more than 0.14, the productivity of film reduces, and in addition, observes the reductions such as bendability sometimes.Planar orientation coefficient can be located in scope by MD multiplying power, heat fixation temperature.In addition, as drawing process, biaxial stretch-formed than simultaneously preferably biaxial stretch-formed successively, biaxial stretch-formed successively particularly preferably in what carry out stretching on TD direction after stretching on MD direction.
In addition, for the variation of the planar orientation coefficient of the width of the film after stretching of the present invention, the total width of its film is divided into 10 equal portions and the difference of the maxima and minima of the planar orientation coefficient recorded is preferably less than 0.02, is more preferably less than 0.015, most preferably is less than 0.01.During more than 0.02, mechanical characteristic has deviation, and in addition, the uneven thickness of film etc. can become large, therefore not preferred.In addition, in order to reduce the variation of this planar orientation coefficient, realized by the difference in specific gravity (difference of degree of crystallinity) of the width reducing non-stretched film.
In addition, the axis of orientation angle of the film after stretching of the present invention is preferably in the scope of 0 ~ 40 degree.In the present invention, the orientation meeting equalization in MD direction and TD direction, but during more than 40 degree, film can deform after the heating, thus not preferred.Therefore, as concrete method, the method bending with common reduction is identical, the method of the contraction in MD direction when reducing the heat fixation after carrying out TD stretching can be adopted, but by reducing the difference of the central part of non-stretched film and the degree of crystallinity of end when casting, can reduce the bending of the end of the film after stretching, be favourable.
The lower limit piercing through intensity of film of the present invention is preferably 0.5N/ μm, is more preferably 0.9N/ μm.During lower than 0.5N/ μm, the intensity of film adding man-hour, when film being formed bag has deficiency.The upper limit piercing through intensity is preferably 1.5N/ μm, and during more than 1.5N/ μm, improving effect can be saturated.Pierce through intensity to be located in scope by MD multiplying power, heat fixation temperature.
The lower limit of the shock strength (shock-resistance) of film of the present invention is preferably 0.05J/ μm, is more preferably 0.06J/ μm.During lower than 0.05J/ μm, when using as bag, intensity has deficiency.The upper limit of shock strength (shock-resistance) is preferably 0.2J/ μm, and during more than 0.2J/ μm, above-mentioned effect of improving can be saturated.
The lower limit of the rate of moisture absorption of film of the present invention is preferably 0.1%, lower than 0.1% time, improving effect can be saturated.The upper limit of rate of moisture absorption is preferably 1%, during more than 1%, easily causes moisture absorption dimensional change etc.
The lower limit of the MD percent thermal shrinkage of film of the present invention is preferably 0.1%, lower than 0.1% time, improving effect can be saturated, in addition, can mechanical property become fragile.The upper limit of MD percent thermal shrinkage is preferably 4%, during more than 4%, can cause spacing skew etc. because printing etc. adds the dimensional change in man-hour.
The lower limit of the TD percent thermal shrinkage of film of the present invention is preferably 0.1%, lower than 0.1% time, improving effect can be saturated, in addition, can mechanical property become fragile.The upper limit of TD percent thermal shrinkage is preferably 3%, and during more than 3%, the dimensional change adding man-hour due to printing etc. can cause the contraction etc. on the width of film.
The lower limit of the mist degree of film of the present invention is preferably 0%.The upper limit of mist degree is preferably 50%, is more preferably 30%, more preferably 20%.As long as be the purposes that cannot see content, just not limited.It should be noted that, when mist degree is more than 30%, can be difficult to when using as bag see content.
Utilize the stacked film of the present invention of dry lamination method and sealing agent and the lower limit of pinhole number that the duplexer obtained is produced by Gelbo torsion test (Gelbo Flex test) is preferably 0.The upper limit of pinhole number is preferably 10, is more preferably 5.During more than 10, when using as bag, film easily forms hole.For the measuring method of pinhole number as aftermentioned.
The application is the right of priority of No. 2012-110536th, the Japan's patent application opinion based on application on May 14th, 2012.The full content of the specification sheets of No. 2012-110536th, Japan's patent application of application on May 14th, 2012 is referred to the application as a reference.
Embodiment
Then, utilize embodiment to illustrate in further detail the present invention, but the present invention is not limited to following example.It should be noted that, the evaluation of film is undertaken by following assay method.
[proportion of non-stretched film]
Shimadzu Seisakusho Ltd. device for measuring specific gravity SGM-300P is used to measure the proportion of each sample at 23 DEG C according to JIS Z8807 8 (in liquid weighing method).
For the difference of width proportion, take the sample of 10 points from the non-stretched film obtained at width, measure proportion by aforesaid method, the maximum value of the result of acquisition is deducted minimum value and the value obtained is tried to achieve divided by minimum value.
[mechanical characteristic (breaking tenacity, elongation at break)]
According to JIS K7113.Razor is used to cut out the sample of width 10mm, length 100mm from film.By the sample that cuts out 23 DEG C, place 12 hours under the atmosphere of 35%RH after, 23 DEG C, under the atmosphere of 35%RH, measure with the condition that chuck spacing 40mm, draw speed 200mm/ divide, use the mean value of 5 measurement results.As the AUTOGRAPH AG5000A that determinator uses company of Shimadzu Seisakusho Ltd. to manufacture.
[planar orientation]
Take the sample of 10 points at width from roller sample.About this sample, according to JISK7142-1996 5.1 (A method), using sodium D-line as light source, utilize Abbérefractometer to measure specific refractory power (nx), the specific refractory power (ny) of width, the specific refractory power (nz) of thickness direction in film length direction, and calculate planar orientation coefficient (Δ P) by following formula.It should be noted that, using the mean value of the planar orientation coefficient of acquisition as planar orientation coefficient.
ΔP＝(nx+ny)/2-nz
The planar orientation coefficient difference of width is set to the difference of the maxima and minima of the sample of above-mentioned 10 points.
[axis of orientation angle]
The MOA-6004 type molecular orientation meter using prince's tester Co., Ltd. to manufacture, tries to achieve the orientation angle (θ) of the molecular chain orientation main shaft of film end.
[shock strength]
Use Toyo Co., Ltd.'s essence mechanism do manufactured by impact tester, under being determined at the atmosphere of 23 DEG C, film is for impacting die-cut intensity.Impact the material that sphere uses diameter 1/2 inch.Unit is J/ μm.
[piercing through intensity]
Test method(s)s such as " 2. " intensity of " food, additive equal-specification benchmark the 3rd: utensil and container package " (No. 20th, the Showa Health and human services department bulletin in 57 years) in based food assanation measure.Pierced through film to pierce through speed 50mm/ minute by the pin of leading section diameter 0.7mm, mensuration pin runs through intensity during film, as piercing through intensity.Carry out under being determined at normal temperature (23 DEG C), unit is N.
[pinhole resistance]
By film of the present invention and sealing agent (TOYOBO Co., LTD. the tensionless winkler foundation Polypropylene film manufactured, P1146, thickness 70 μm), use 33.6 mass parts polyester polyol (Toyo-Morton, Ltd. manufacture, TM-509), 4.0 mass parts polyisocyanates (Toyo-Morton, Ltd. manufacture, CAT-10L) and the polyurethane binding that is obtained by mixing of 62.4 mass parts ethyl acetate carry out dry lamination, make duplexer.
Above-mentioned duplexer is cut to the size of 20.3cm (8 inches) × 27.9cm (11 inches), by the rectangle test film after this cut-out under the condition of temperature 23 DEG C, relative humidity 50%, place and within more than 24 hours, carry out modulating (conditioning).Then, this rectangle test film rolling is become the cylindrical shape of length 20.32cm (8 inches).And, one end of its cylindrical thin-film is fixed on the periphery of the discoid fixed head of Gelbo torsion test instrument (Rigaku Corporation manufacture, NO.901 type) (specification according to MIL-B-131C), the other end of cylindrical thin-film is fixed on the periphery of the discoid moving head separating 17.8cm (7 inches) and relative tester with fixed head.Then, make moving head the direction of fixed head along parallel relative two the nearly 7.6cm that is coupling (3 inches) during rotate 440 ゜, then non rotating and after the 6.4cm that keeps straight on (2.5 inches), these action reversed are carried out, moving head is made to get back to initial position, pliability test is carried out, within every 1 minute, to implement speed 1000 circulations repeatedly continuously of 40 circulations as 1 circulation.Implement to carry out at 5 DEG C.Then, remove the part being fixed on the periphery of fixed head and moving head of tested film, the pinhole number measuring the part generation in 17.8cm (7 inches) × 27.9cm (11 inches) (that is, measures every 497cm
2the pinhole number of (77 square inches)).
[limiting viscosity of polyester]
0.1g polyester is made to be dissolved in phenol/tetrachloroethane (volumetric ratio: in 25mL mixed solvent 3/2), use the limiting viscosity of Ostwald viscometer determining polyester at 30 DEG C.
[fusing point of polyester]
The differential scanning type calorimeter (DSC) using SII Corporation to manufacture, measures under sample size 10mg, heat-up rate 20 DEG C/min.Wherein, using the melting endotherm peak temperature that the detects fusing point as polyester.
[thickness]
The method according to JIS-Z-1702 is utilized to measure the thickness of film.
[percent thermal shrinkage]
Setting test temperature 150 DEG C, 10 minutes heat-up times, in addition, the dimensional change test method determination percent thermal shrinkage utilizing JIS-C-2318 to record.
[mist degree]
Utilize the method according to JIS-K-7105, use haze meter (NIPPON DENSHOKU INDUSTRIE Co., LTD. manufacture, NDH2000) to measure the mist degree of sample different 3 positions, using its mean value as mist degree.
[homogeneity (Tv (%)) of thickness]
Cut out diaphragm from the central part of the film roll obtained along longitudinal direction, use dial gauge to measure the thickness of film with 5cm spacing, calculate to obtain the homogeneity of thickness from its result.
[stripping strength]
By film of the present invention and sealing agent (TOYOBO Co., LTD. the tensionless winkler foundation Polypropylene film manufactured, P1146, thickness 70 μm), use 33.6 mass parts polyester polyol (Toyo-Morton, Ltd. manufacture, TM-509), 4.0 mass parts polyisocyanates (Toyo-Morton, Ltd. manufacture, CAT-10L) and the polyurethane binding that is obtained by mixing of 62.4 mass parts ethyl acetate carry out dry lamination, make duplexer.
Above-mentioned duplexer is cut to width 15mm, length 200mm as coupons, use Toyo Baldwin Co., LTD. " the Tension UMT-II-500 type " that manufacture, under the condition of temperature 23 DEG C, relative humidity 65%, be determined at the stripping strength on untreated of polyester film and the junction surface of polyolefin resin interlayer.It should be noted that, setting draw speed is 10cm/ minute, peel angle is 180 degree.
[rate of moisture absorption]
Film of the present invention is cut to the square of length of side 50mm, utilizes the method according to JIS-K-7209-7.2.1 (A method), measure to be immersed in and keep temperature to be the changes in weight of the film before and after the water of 23 DEG C ± 2 DEG C.Rate of moisture absorption is calculated by following formula (1).
Rate of moisture absorption (%)=100 × ([M2]-[M1])/[M1] (1)
It should be noted that, in above-mentioned formula (1), [M1] is the film weight before immersion, and [M2] is the film weight after immersion.
[embodiment 1]
Use twin screw vented extruders, add the masterbatch containing PBT resin (Mitsubishi Engineering-Plastics manufactures NOVADURAN5020, fusing point 220 DEG C) and the calcium carbonate as lubricant, compounding one-tenth lubricant concentration is 2000ppm, by the melting at 270 DEG C of gained material, cast from the T-mould of 270 DEG C afterwards, utilize the closely sealed method of electrostatic to make it be sealed at the cooling roller of 0 DEG C, obtain non-stretched film.For the surface temperature of cooling roller, carry out measuring (thermopair) with 10cm interval at width, its deviation of result is less than 3 DEG C.Then, at 60 DEG C, carry out 3.2 times of rollers along longitudinal direction stretch, secondly, utilize tenter machine to carry out 3 times of stretchings along transverse direction at 80 DEG C, at 200 DEG C, implement nervous thermal treatment in 3 seconds and after within 1 second, relaxing process, cut off and remove both ends thus obtain the PBT film that thickness is 12 μm.The film forming condition of the film of acquisition, physical property and evaluation result are shown in table 1.It should be noted that, the axis of orientation angle of film end is 35 degree, and the distortion of the sample after percent thermal shrinkage measures is small.
[embodiment 2]
Use twin screw vented extruders, add the masterbatch containing PBT resin (Mitsubishi Engineering-Plastics manufactures NOVADURAN5020) and the calcium carbonate as lubricant, compounding one-tenth lubricant concentration is 2000ppm, by the melting at 270 DEG C of gained material, afterwards melting pipeline is directed into the static mixer (STMX) of 12 elements.Thus, carry out the segmentation of PBT molten mass/stacked, obtain the multilayered molten body formed by identical raw material.Afterwards, be directed into the T-mould of 270 DEG C and cast, utilizing the closely sealed method of electrostatic to make it be sealed at the cooling roller of 15 DEG C, obtaining non-stretched film.For the surface temperature of cooling roller, carry out measuring (thermopair) with 10cm interval at width, its deviation of result is less than 3 DEG C.Then, at 60 DEG C, carry out 3.8 times of rollers along longitudinal direction stretch, secondly, utilize tenter machine to carry out 3 times of stretchings along transverse direction at 65 DEG C, implement the mitigation process of the nervous thermal treatment of 3 seconds and 1 second at 200 DEG C after, cut off and remove both ends thus acquisition thickness is the PBT film of 12 μm.The film forming condition of the film of acquisition, physical property and evaluation result are shown in table 1.It should be noted that, the axis of orientation angle of film end is 25 degree, and the distortion of the sample after percent thermal shrinkage measures is small.
[embodiment 3 ~ 4]
The condition recorded by table 1 obtains film.The film forming condition of the film of acquisition, physical property and evaluation result are shown in table 1.It should be noted that, Ecoflex (logging in business Standard) employs poly-(tetramethylene adipate-co-mutual-phenenyl two acid bromide two alcohol ester) multipolymer (PBAT) that BASF JAPAN LTD. manufactures.
[table 1]
[comparative example 1]
Chill-roll temperature during setting casting is 15 DEG C, in addition, and the means discussion filming recorded with embodiment 1.Film forming condition shown in table 2.Non-stretched film ruptures when MD stretches, and fails to obtain film.
[comparative example 2]
The condition recorded by table 2 obtains film.The film forming condition of the film of acquisition, physical property and evaluation result are shown in table 2.
[comparative example 3]
Use the non-stretched film of the condition acquisition recorded by table 2 as sample.The mode being 20 μm with thickness adjusts winding speed to manufacture film.It should be noted that, the axis of orientation angle of film end is less than 5 degree, and distortion do not observed by the sample after percent thermal shrinkage measures.
[comparative example 4]
Use TOYOBO Co., ester (TOYOBO ESTER) (registered trademark) film E5100 (thickness 12 μm) spins in Japan that LTD. manufactures.
[reference example 1]
Representatively PBT film, uses the PBT film that commercially available Kansai Chemicals Co., Ltd. manufactures.The axis of orientation angle of film end is less than 5 degree, and distortion do not observed by the sample after percent thermal shrinkage measures.
[table 2]
utilizability in industry
For polyester film of the present invention, in order to the fracture caused when the PBT suppressing crystallization velocity large stretches, particularly by suppress the molten resin that width is discharged from mould velocity of shear, casting time the degree of crystallinity inequality homogenize that causes of the difference of speed of cooling, in the difference in specific gravity of width during reduction unstretched state, fracture when stretching can be suppressed thus significantly.The present invention can industrially implement, and can improve the harmony, shock-resistance etc. of the mechanical characteristic in MD and TD direction.
Claims (5)
1. a polyester film, it is formed by the vibrin comprising the above polybutylene terephthalate of 60 quality %, and the elongation at break of MD is more than 80%, the elongation at break of TD is more than 80%, planar orientation is 0.12 ~ 0.14, shock strength is more than 0.05J/ μm and to pierce through intensity be more than 0.5N/ μm.
2. polyester film according to claim 1, wherein, is divided into 10 equal portions by the total width of film after stretching and the difference of the maxima and minima of planar orientation coefficient that records is less than 0.02.
3. polyester film according to claim 1 and 2, wherein, the difference of the maxima and minima of the thickness in the total width of the film after stretching is 0 ~ 25% relative to mean thickness.
4. a manufacture method for polyester film, the method for its polyester film according to any one of manufacturing claims 1 ~ 3, is characterized in that, when casting to cooling roller, the difference of the degree of crystallinity of width is reduced.
5. manufacture method according to claim 4, is characterized in that, the method that the difference of the degree of crystallinity of width is reduced is: carry out to the casting of cooling roller at low temperatures and/or the raw material of same composition is carried out multiple stratification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810810311.2A CN109111585A (en) | 2012-05-14 | 2013-05-07 | The manufacturing method of polyester film |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2012-110536 | 2012-05-14 | ||
| JP2012110536 | 2012-05-14 | ||
| PCT/JP2013/062812 WO2013172214A1 (en) | 2012-05-14 | 2013-05-07 | Polyester film and method for producing same |
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| CN201810810311.2A Division CN109111585A (en) | 2012-05-14 | 2013-05-07 | The manufacturing method of polyester film |
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| CN104321372B CN104321372B (en) | 2018-07-06 |
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| CN201380025562.5A Active CN104321372B (en) | 2012-05-14 | 2013-05-07 | Polyester film and its manufacturing method |
| CN201810810311.2A Withdrawn CN109111585A (en) | 2012-05-14 | 2013-05-07 | The manufacturing method of polyester film |
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| CN201810810311.2A Withdrawn CN109111585A (en) | 2012-05-14 | 2013-05-07 | The manufacturing method of polyester film |
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| Country | Link |
|---|---|
| JP (2) | JP6194629B2 (en) |
| KR (1) | KR101961002B1 (en) |
| CN (2) | CN104321372B (en) |
| MY (1) | MY172893A (en) |
| TW (1) | TWI622608B (en) |
| WO (1) | WO2013172214A1 (en) |
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| CN110494476A (en) * | 2017-03-28 | 2019-11-22 | 东洋纺株式会社 | Biaxially oriented polyester film and its manufacturing method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0216029A (en) * | 1988-07-04 | 1990-01-19 | Unitika Ltd | Polyester biaxially oriented film |
| JPH05200860A (en) * | 1992-01-29 | 1993-08-10 | Okura Ind Co Ltd | Heat-resistant bag |
| CN101600977A (en) * | 2007-01-31 | 2009-12-09 | 东洋纺织株式会社 | Surface light-diffusing polyester film |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5234923B2 (en) | 1974-10-02 | 1977-09-06 | ||
| JPS51146572A (en) | 1975-06-12 | 1976-12-16 | Asahi Chemical Ind | Two dimensional elongation poly butylene terephthalate films |
| JPS5712612A (en) * | 1980-06-26 | 1982-01-22 | Nippon Synthetic Chem Ind Co Ltd:The | Stretching method for film of saponified ethylene-vinyl acetate copolymer |
| JP3150441B2 (en) * | 1992-08-04 | 2001-03-26 | 大倉工業株式会社 | Polybutylene terephthalate resin composition for tubular biaxially oriented film with excellent stretching stability |
| JP3316913B2 (en) * | 1992-10-26 | 2002-08-19 | 東レ株式会社 | Heat-sealable polyester film and method for producing the same |
| US5968666A (en) * | 1996-03-08 | 1999-10-19 | 3M Innovative Properties Company | Multilayer polyester film |
| EP0929599B1 (en) * | 1996-09-24 | 2001-12-05 | Mitsubishi Polyester Film GmbH | Biaxially-oriented pet foil for use for smd foil capacitors, method for the production of said foil and its use as foil capacitors in smd technology |
| JP3247053B2 (en) * | 1996-10-09 | 2002-01-15 | ユニチカ株式会社 | Polyester film for metal plate lamination and method for producing the same |
| JP2001504047A (en) * | 1997-08-21 | 2001-03-27 | ミツビシ ポリエステル フィルム ジーエムビーエイチ | Biaxially stretched PET film for SMD film capacitor with improved mechanical and shrinkage properties and method for producing the same |
| JP2003073488A (en) * | 2001-06-20 | 2003-03-12 | Mitsubishi Chemicals Corp | Polybutylene terephthalate-based resin oriented film, multi-layered oriented film and bag-like packaging material with the same |
| JP3709869B2 (en) | 2002-01-11 | 2005-10-26 | 東洋紡績株式会社 | Polyester film |
| JP3680833B2 (en) * | 2002-01-11 | 2005-08-10 | 東洋紡績株式会社 | Production method of polyester film |
| JP4273855B2 (en) | 2002-08-08 | 2009-06-03 | 東レ株式会社 | Laminated film and packaging film |
| JP4341555B2 (en) * | 2002-09-10 | 2009-10-07 | 東レ株式会社 | Biaxially oriented polyester film |
| JP2005179486A (en) * | 2003-12-19 | 2005-07-07 | Mitsubishi Polyester Film Copp | Highly transparent polyester film for optical use |
| JP2007301982A (en) * | 2006-04-12 | 2007-11-22 | Toray Ind Inc | Laminated polyester film |
| JP2010069830A (en) * | 2008-09-22 | 2010-04-02 | Fujifilm Corp | Method of manufacturing unextended polymer molding, method of manufacturing cavity-containing resin molding using the unextended polymer molding, and cavity-containing resin molding obtained by the manufacturing method |
| JP5421045B2 (en) * | 2008-10-01 | 2014-02-19 | 富士フイルム株式会社 | Film and film manufacturing method |
| JP5267817B2 (en) * | 2008-12-03 | 2013-08-21 | 東洋紡株式会社 | Thermoplastic resin stretched multilayer film with layered compound highly oriented in plane |
| JP6032780B2 (en) * | 2010-12-09 | 2016-11-30 | 興人フィルム＆ケミカルズ株式会社 | Biaxially stretched polybutylene terephthalate film |
| JP5177244B2 (en) * | 2011-02-16 | 2013-04-03 | 東洋紡株式会社 | Heat-shrinkable polyester film and method for producing the same |
| KR101961002B1 (en) * | 2012-05-14 | 2019-03-21 | 도요보 가부시키가이샤 | Polyester film and method for producing same |
| KR102071745B1 (en) * | 2012-11-16 | 2020-01-30 | 도요보 가부시키가이샤 | Biaxially oriented polyester film and method for producing same |
-
2013
- 2013-05-07 KR KR1020147031598A patent/KR101961002B1/en active IP Right Grant
- 2013-05-07 CN CN201380025562.5A patent/CN104321372B/en active Active
- 2013-05-07 WO PCT/JP2013/062812 patent/WO2013172214A1/en active Application Filing
- 2013-05-07 CN CN201810810311.2A patent/CN109111585A/en not_active Withdrawn
- 2013-05-07 MY MYPI2014703346A patent/MY172893A/en unknown
- 2013-05-10 JP JP2013100065A patent/JP6194629B2/en active Active
- 2013-05-13 TW TW102116821A patent/TWI622608B/en active
-
2016
- 2016-06-17 JP JP2016120798A patent/JP6202146B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0216029A (en) * | 1988-07-04 | 1990-01-19 | Unitika Ltd | Polyester biaxially oriented film |
| JPH05200860A (en) * | 1992-01-29 | 1993-08-10 | Okura Ind Co Ltd | Heat-resistant bag |
| CN101600977A (en) * | 2007-01-31 | 2009-12-09 | 东洋纺织株式会社 | Surface light-diffusing polyester film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105682893A (en) * | 2013-11-13 | 2016-06-15 | 东洋纺株式会社 | Biaxially stretched polyester film and method for producing same |
| CN109070571A (en) * | 2016-03-30 | 2018-12-21 | 东洋纺株式会社 | Vacuum heat insulation materials laminated body |
| CN110494476A (en) * | 2017-03-28 | 2019-11-22 | 东洋纺株式会社 | Biaxially oriented polyester film and its manufacturing method |
| CN112805137A (en) * | 2018-10-05 | 2021-05-14 | 东洋纺株式会社 | Biaxially oriented polyamide film and rolled polyamide film roll |
| CN113692343A (en) * | 2019-04-11 | 2021-11-23 | 巴斯夫欧洲公司 | Thermal forming method for polybutylene terephthalate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104321372B (en) | 2018-07-06 |
| WO2013172214A1 (en) | 2013-11-21 |
| JP2013256110A (en) | 2013-12-26 |
| CN109111585A (en) | 2019-01-01 |
| KR101961002B1 (en) | 2019-03-21 |
| MY172893A (en) | 2019-12-13 |
| KR20150008872A (en) | 2015-01-23 |
| JP6202146B2 (en) | 2017-09-27 |
| JP6194629B2 (en) | 2017-09-13 |
| JP2016172454A (en) | 2016-09-29 |
| TW201406831A (en) | 2014-02-16 |
| TWI622608B (en) | 2018-05-01 |
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