CN109111585A - The manufacturing method of polyester film - Google Patents
The manufacturing method of polyester film Download PDFInfo
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- CN109111585A CN109111585A CN201810810311.2A CN201810810311A CN109111585A CN 109111585 A CN109111585 A CN 109111585A CN 201810810311 A CN201810810311 A CN 201810810311A CN 109111585 A CN109111585 A CN 109111585A
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- film
- stretched
- raw material
- pbt
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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
-
- 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
-
- 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
Abstract
The manufacturing method of Biaxially oriented polyester film is provided, it is the manufacturing method of the Biaxially oriented polyester film stretched to non-stretched film, the non-stretched film is obtained from the raw material progress multiple stratification of same composition is cast again, the raw material is the polyester resin that the containing ratio of polybutylene terephthalate (PBT) is 60 mass % or more, the multiple stratification is using only one extruder and imported into extruder to the multilayer device of the melt line between mold and carries out, and is 8 layers or more by the number of plies that multiple stratification is formed.
Description
The application be the applying date be on May 07th, 2013, application No. is 2013800255625, entitled " polyester
The divisional application of the application of film and its manufacturing method ".
Technical field
The present invention relates to polyester film and its manufacturing methods.Systems be suitable for using nylon film at present
Or harmonious excellent polyester film and its system of the purposes of other soft films, impact resistance, bendability, mechanical strength
Make method.
Background technique
The mechanical characteristic of polybutylene terephthalate (PBT) (PBT), excellent impact resistance, therefore it is used as engineering plastics so far
It uses, also as useful materials'use from the aspect of especially from crystallization rate, fast, productivity is excellent.However, PBT is due to knot
Brilliant speed is fast, biaxial stretch-formed difficulty.This is because, the orientation of drawing process causes to crystallize, cause to stretch difficult.Relative to
This, in order to play the PBT characteristic that has originally, carried out since past 40 years with using biaxial stretching improve planar orientation from
And the mechanical characteristic as film, the research for the purpose of impact resistance are improved, but so far, commercially available PBT film is still not draw
The cast sheet stretched and the film obtained using inflation method, the orientation of the PBT of these films is insufficient, and therefore, it is difficult to say to have played
The characteristic of the PBT of script.Especially for the PBT film obtained using inflation method, since its manufacturing method causes to stretch again
Rate is difficult to uniformly, there is a problem of that thickness and precision is bad, and then since surface orientation coefficient can not be got higher, it is low that there is also puncture intensities
The problems such as.Therefore, the PBT film obtained to the biaxial stretching process carried out using stenter is studied.Hereinafter, for the past
The research of PBT film carry out some discussion.
At present it is known that there is following technology: in a manner of making 3.5 times of stretching ratio below after the side TD is pulled up, with
The deformation velocity of 100000%/min or more stretches to manufacture biaxial stretch-formed PBT film in the MD direction, so that manufacture is uniformly drawn
The technology for the film without uneven thickness stretched (for example, see patent document 1).However, knot of the prior art from embodiment
There are the following problems known to fruit: the deformation velocity due to only accelerating the direction MD, elongation can be low, can not become in the direction MD and TD
Direction obtains balanced film.
Furthermore it is known that there is following technology: be based on experimental result, by it is non-stretched when crystallinity calculate draft temperature, herein
After the stretching for more than temperature implementing the direction MD (or TD) with low range, at high temperature orthogonal with the draw direction of first stage
Direction stretched, the film for the excellent impact resistance that fracture is inhibited when thus manufacturing uneven thickness, film (such as is joined
See patent document 2).However, for the prior art, from the side of the Tg (45 DEG C) for being stretched as 120 DEG C and PBT of second stage
Face considers, is stretching at higher temperatures, is that the state for having carried out oriented crystalline can be taken again in the direction of second stage
To such stretching, therefore there is a problem of that the harmony of the mechanical characteristic in the direction MD and the direction TD is bad.
It has been known that there is following technologies: by by PBT and polyethylene terephthalate (PET), poly- naphthalenedicarboxylic acid ethylene glycol
Resin other than the PBT such as ester (PEN) carry out it is alternately laminated, thus manufacture the excellent film of gas barrier property, pinhole resistance (for example, see
Patent document 3).However, the layer that PET, PEN resin other than the prior art stacking PBT are formed, therefore become draft temperature
Stretching under the draft temperature of PET, the PEN of Tg higher than PBT is stretching at high temperature from the point of view of the Tg of PBT.Therefore, do not have
There is the feature for the PBT film for playing script, and the resin group in film becomes two kinds, cutting chip when therefore, it is difficult to be film-made
It is recycled etc. being again added in raw material, there is a problem of that economic aspect is unfavorable.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 51-146572 bulletin
Patent document 2: Japanese Unexamined Patent Application 51-40904 bulletin
Patent document 3: No. 4273855 bulletins of Japanese Patent No.
Summary of the invention
Problems to be solved by the invention
The present invention is completed using the problem of the prior art as background.That is, it is an object of the invention to: in order to press down
The fast PBT of crystallization rate processed caused fracture when stretching, the melting being discharged in width direction from mold especially by inhibition
Crystallinity caused by the difference of cooling velocity when the shear velocity of resin, casting it is uneven, reduce the non-stretched of film
Thus the difference in specific gravity in the direction of the width of state provides and significantly inhibits fracture, can industrially implement, the direction MD/TD
Harmony, the impact resistance of mechanical characteristic etc. improve excellent polyester film and its manufacturing method.
The solution to the problem
The inventors of the present invention in order to achieve the above object, have made intensive studies, and as a result complete the present invention.
That is, the present invention is a kind of polyester film, formed by the polyester resin comprising the 60 above PBT of mass %, MD's is disconnected
Split that elongation is 80% or more, the elongation at break of TD is 80% or more, planar orientation is 0.12~0.14, impact strength is
0.05J/ μm or more and puncture intensity are 0.5N/ μm or more.
The effect of invention
According to the present invention, in polyester film and its manufacturing method, in order to which the PBT for inhibiting crystallization rate fast draws when stretching
The fracture risen, especially by the cooling inhibited in shear velocity, the casting for the molten resin that width direction is discharged from mold
Crystallinity caused by the difference of speed is uneven, reduces the difference in specific gravity in the direction of the width of film unstretched state, thus greatly
Fracture when amplitude inhibits film to stretch, can industrially implement, and can improve the mechanical characteristic in MD and TD direction
Harmony, impact resistance etc..
Specific embodiment
Hereinafter, the present invention will be described in detail.
The polyester resin that the present invention uses using PBT as main composition, the containing ratio of PBT be preferably 60 mass % with
It upper, further preferably 70 mass % or more, particularly preferably 75 mass % or more, is most preferably 80 mass % or more.It is lower than
When 60 mass %, the impact strength and pinhole resistance of film are reduced, and film characteristics are simultaneously insufficient.
For as PBT used in main composition, as dicarboxylic acid component, terephthalic acid (TPA) be 90 moles of % with
On be preferred, be most preferably more preferably 95 moles of % or more, further preferably 98 moles of % or more, 100 moles of %.Make
For glycol component, 1,4-butanediol is that 90 moles of % or more are preferred, more preferably 95 moles of % or more, further preferably
For 97 moles of % or more, do not include most preferably when polymerizeing by the substance other than the by-product of the ehter bond generation of 1,4- butanediol.
It as the dicarboxylic acid component that can be copolymerized, can enumerate: M-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, biphenyl
Dicarboxylic acids, cyclohexane dicarboxylic acid, adipic acid, azelaic acid, decanedioic acid etc..As the glycol component that can be copolymerized, can enumerate:
Ethylene glycol, 1,3- propylene glycol, 1,2- propylene glycol, neopentyl glycol, 1,5- pentanediol, 1,6-HD, diethylene glycol, hexamethylene two
Alcohol, polyethylene glycol, polytetramethylene glycol, polycarbonate glycol etc..
These need be able to satisfy with aftermentioned other polyester resin, additive amount between harmony and film impact
Intensity, the range of puncture intensity, adjust the copolymerization amount of each monomer.
In addition, being not particularly limited as other constituents, can be added in the polyester resin poly- to benzene two
Formic acid glycol ester (PET), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), poly- terephthaldehyde
Acid propylene glycol ester (PPT) etc., other polyester resin, as additive, be bent for improving when pinhole resistance and make soft
Polyester and polyamide-based bullet obtained from the copolymerization of any one of soft polyether components, polycarbonate component, polyester component
Property body.
The lower limit of the additive amount of these additives is preferably 0 mass %, and the upper limit is preferably 20 mass %.When more than 20%,
Said effect saturation, in addition to this, the transparency of film can be caused to reduce etc..
The lower limit of resin melt temperature is preferably 200 DEG C, and when being 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, when more than 320 DEG C, can cause the deterioration of resin.
Aforementioned polyester resin can contain currently known additive, such as lubricant, stabilizer, coloring as needed
Agent, antioxidant, antistatic agent, ultraviolet absorbing agent etc..
As lubricant type, the preferably inorganic system such as organic lubricant, silica, calcium carbonate, aluminium oxide lubricates material
Material, more preferable silica, calcium carbonate, particularly preferred calcium carbonate.Thus, it is possible to embody the transparency and sliding property of film.
The lower limit of lubricant concentration is preferably 100ppm, and when being lower than 100ppm, the sliding property of film can be reduced.Lubricant is dense
The upper limit of degree is preferably 20000ppm, and when more than 20000ppm, the transparency of film can be reduced.
As the key for obtaining film of the present invention, need to reduce the knot of the width direction of non-stretched film in casting
The difference of brilliant degree.Therefore, as specific method, it can enumerate and cast to the chill roll of low temperature.In addition, in order to it is cooling not with
The face of chill roll contact may also set up contact roller to improve cooling efficiency.
In addition, the inventors of the present invention's discovery: can reduce by using aftermentioned novel method and do not draw as other methods
The crystallinity for stretching the width direction of film is poor.I.e., it was found that in casting by carrying out the raw material multiple stratification of same composition again
Casting, can reduce the difference of the crystallinity of the width direction of non-stretched film, tensile stress when TD can be made to stretch is evenly distributed.Mesh
Before, in casting, the crystallinity of the end of non-stretched film is got higher, and the crystallinity of the central portion of non-stretched film is lower, therefore
When the direction TD stretches, tensile stress becomes unevenly in the width direction of non-stretched film, so that film is easily broken off, because
This, needs to carry out TD stretching at higher temperatures.In contrast, although the reason is to speculate, even if by same resin layers
There is also the interfaces of layer when folded, accelerate because crystallizing caused by the interface, on the other hand, it is believed that more than layer big crystallization by
Inhibit, therefore the crystallinity of the width direction in non-stretched film becomes uniform.As specific method, can be used common
Multilayer device (multilayer supply head, static mixer, multilayer branch manifold etc.), such as will never using two or more extruders
The method etc. for being laminated for multilayer using supply head, static mixer, multi-manifold etc. with the thermoplastic resin that flow path is sent out.It needs
It is noted that an extruder can be used only, above-mentioned multilayer device be led when by the raw material multiple stratification of same composition
Enter to extruder to the melt line (melt line) between mold, thus reaches the purpose of the present invention.
It should be noted that the raw material of same composition refers to, when using two or more extruders, set from each extrusion
In the content for each raw material being compounded in the thermoplastic resin that machine is sent out, the difference of biggest quality % and minimum mass % allow for 10
It quality % or less, is further 5 mass % or less, specifically for 2 mass % or less.When polyester uses copolymer, setting is squeezed from each
In the content of the monomer for the copolymerization being compounded in the thermoplastic resin that machine is sent out out, maximum mole % and the difference of minimum mole % are allowed
For 5 moles of % or less, be further 3 moles of % or less, specifically for 2 moles of % or less.In addition, the molecular weight of each raw material can also
With difference, but when acquiring the weight average molecular weight of styrene conversion by GPC, with the difference substance big divided by molecular weight of its molecular weight
Molecular weight value be preferably 30% or less, as long as further preferably 20% or less, particularly preferably 10% hereinafter, in the model
It encloses, even if the molecular weight of each raw material is different, also allows as identical each raw material.
Above-mentioned multilayer device is imported into extruder to melting between mold it should be noted that an extruder is used only
The method for melting pipeline, the management aspect consideration from the simplicity, each raw material of device is also preferred method.
The lower limit of mold temperature is preferably 200 DEG C, and when being lower than 200 DEG C, the discharge of molten resin is unstable, the thickness of film
It can become uneven.The upper limit of mold temperature is preferably 350 DEG C, when more than 350 DEG C, in addition to the thickness of film become unevenly with
Outside, the deterioration of resin can also be caused, because die lip pollution etc. causes bad order.
The lower limit of chill-roll temperature is preferably -10 DEG C, when being lower than -10 DEG C, the crystallinity of the width direction of non-stretched film
Uniformization effect saturation.The upper limit of chill-roll temperature is preferably 80 DEG C, and when more than 80 DEG C, the crystallinity of non-stretched film becomes
It is excessively high to be become difficult to stretch.In order to reduce non-stretched film width direction crystallinity difference, reduce crystallinity be to have
Effect, from this viewpoint, when without using the method for aftermentioned multiple stratification etc., chill-roll temperature is preferably 10 DEG C or less, into
One step is 5 DEG C or less.At this point, condensing in order to prevent, the ambient humidity near chill roll is preferably reduced.On the other hand, Ke Yitong
The crystallinity for crossing using the methods of aftermentioned multiple stratification the width direction for reducing non-stretched film is poor, at this point, even if 15~
It can also cast at a temperature of 40 DEG C.
The temperature difference of the width direction of chill roll is smaller to be preferred, and preferable temperature difference is 5 DEG C or less, further preferably 3 DEG C
Below.In the case that temperature difference is more than 5 DEG C, the crystallinity of the width direction of non-stretched film in casting can not be reduced sometimes
Difference.
In casting, the temperature of cooling roller surface is caused to rise since surface contacts the resin of high temperature.In general, chill roll
Cooling water is circulated to be cooled down by piping internal, but is the need to ensure that sufficient cooling water inflow, designs matching for piping
It sets, repair so as to not have to adhere to the temperature difference of the width direction to reduce cooling roller surface such as sludge in piping.Especially
Be the method for multiple stratification etc. is not used and it is cooling at low temperature when need to pay attention to.
When the casting of multilayered structure, at least 3 layers or more, preferably 5 layers or more, more preferably 8 layers or more, most preferably
100 layers or more.When the number of plies is few, the difference in specific gravity of the width direction of non-stretched film becomes larger, and the improvement of draftability is small.For
At 100 layers or more, reduce the effect stability of the difference in specific gravity of the width direction of non-stretched film, in addition to this, the thickness of each layer is equal
Even property is also stable, it may have appearance investigation and other effects, therefore it is preferred that.
Then drawing process is illustrated.It can may be successively double for simultaneously biaxial drawing for drawing process
Axis stretches, but in order to improve the puncture intensity of film, needs to improve the surface orientation coefficient of film, from this viewpoint preferably according to
It is secondary biaxial stretch-formed.
The lower limit of MD draft temperature is preferably 40 DEG C, more preferably 45 DEG C.When lower than 40 DEG C, fracture is easily caused.MD is drawn
The upper limit for stretching temperature is preferably 100 DEG C, more preferably 95 DEG C.When more than 100 DEG C, sometimes because being difficult to lead to the power of film due to orientation
Learning characteristic reduces.
The lower limit of MD stretching ratio is preferably 2.5 times, when being lower than 2.5, sometimes because being difficult to lead to the mechanics of film due to orientation
Characteristic, uneven thickness deteriorate.The upper limit of MD stretching ratio is preferably 5 times, when more than 5 times, improves mechanical strength, the thickness of film
Uneven effect can be saturated.
The lower limit of TD draft temperature is preferably 40 DEG C, when being lower than 40 DEG C, easily causes the fracture of film.TD draft temperature
The upper limit is preferably 100 DEG C, when more than 100 DEG C, sometimes because being difficult to cause the mechanical characteristic of film to reduce due to orientation.
The lower limit of TD stretching ratio is preferably 2.5 times, when being lower than 2.5 times, sometimes because be difficult to cause due to orientation mechanical characteristic,
Uneven thickness deteriorates.The upper limit of TD stretching ratio is preferably 5 times, when more than 5 times, improves mechanical strength, the uneven thickness of film
Effect can be saturated.
The lower limit of TD heat-fixing temperature is preferably 150 DEG C, and when being lower than 150 DEG C, the percent thermal shrinkage of film becomes larger, and causes to process
When offset, shrink.The upper limit of TD heat-fixing temperature is preferably 250 DEG C, when more than 250 DEG C, thin film melt, in addition to this, i.e.,
Making not melt can also become fragile.
The lower limit of TD relaxation rate is preferably 0.5%, and when being lower than 0.5%, the fracture of film is easily caused in heat fixation.TD
The upper limit of relaxation rate is preferably 10%, and when more than 10%, film generates relaxation etc. to which uneven thickness occur.
For it is of the invention it is biaxial stretch-formed after film, the lower limit of film thickness is preferably 3 μm, more preferably 5 μm, into one
Preferably 8 μm of step.It, can be insufficient as thin film strength when lower than 3 μm.The upper limit of film thickness is preferably 100 μm, is more preferably
75 μm, further preferably 50 μm.When more than 100 μm, film becomes blocked up and the processing in the purpose of the present invention is caused to become
It is difficult.
About the uneven thickness in overall width of roller, the difference of maximum gauge and minimum thickness in overall width is relative to average thickness
Degree is preferably in 0~25% range, is more preferably in 0~20% range.When more than 25%, can generate roller bad order,
Caused deformation etc. when secondary operation, it is not preferable.In order to reduce the difference of maximum gauge and minimum thickness in overall width, need
Keep the stretching ratio of width direction uniform, crystallinity when therefore, it is necessary to make non-stretched in advance is uniform.
The lower limit of the specific gravity of the central portion of non-stretched film of the invention is preferably 1.25g/cm3, it is lower than 1.25g/cm3When,
The effect for improving the draftability of non-stretched film can be saturated.The upper limit of the specific gravity of central portion is preferably 1.3g/cm3, more than 1.3g/
cm3When, crystallinity becomes excessively high difficult so as to cause stretching.
The upper limit of the difference of the width direction specific gravity of non-stretched film of the invention is preferably 0.03g/cm3, more than 0.03g/
cm3When, the tensile stress of width direction is uneven, so as to cause film fracture, cause film width direction stretching not
, become the reason of uneven thickness, physical property unevenness.
The lower limit of the MD elasticity modulus of film of the invention is preferably 1GPa, and when being lower than 1GPa, film is easy elongation, is being printed
It can cause spacing (pitch) offset etc. when the processing such as brush, lamination.The upper limit of MD elasticity modulus is preferably 2GPa, when more than 2GPa,
After film and various sealants etc. are bonded, it is unfavorable to have in terms of the processabilities such as drawing process.
The lower limit of the TD elasticity modulus of film of the invention is preferably 1GPa, and when being lower than 1GPa, film is easy elongation, is being added
Working hour can cause problem.The upper limit of TD elasticity modulus is preferably 2GPa, and when more than 2GPa, film and various sealants etc. are bonded
Afterwards, it is unfavorable to have in terms of the processabilities such as drawing process.It should be noted that TD elasticity modulus can be set by heat-fixing temperature
In range.
The lower limit of the TD breaking strength of film of the invention is preferably 100MPa, when being lower than 100MPa, when the processing of film
It can cause fracture etc..The upper limit of TD breaking strength is preferably 500MPa, when more than 500MPa, improves the effect of the breaking strength of film
Fruit can be saturated.
The lower limit of the MD elongation at break of film of the invention is preferably 80%, more preferably 90%.It is thin when lower than 80%
After film and various sealants etc. are bonded, it is unfavorable to have in terms of the processabilities such as drawing process.The upper limit of MD elongation at break does not have
Special limitation, preferably 200%.MD elongation at break can be located in range by MD multiplying power, heat-fixing temperature.
The lower limit of the TD elongation at break of film of the invention is preferably 80%, more preferably 90%.It is thin when lower than 80%
After film and various sealants etc. are bonded, it is unfavorable to have in terms of the processabilities such as drawing process.The upper limit of TD elongation at break does not have
Special limitation, preferably 500%.TD elongation at break can be located in range by TD multiplying power, heat-fixing temperature.
The lower limit of the surface orientation coefficient of film of the invention is preferably 0.12, when being lower than 0.12, puncture intensity, impact strength
Etc. can reduce.The upper limit of surface orientation coefficient is preferably 0.14, and when more than 0.14, the productivity of film is reduced, in addition to this, sometimes
It can observe the reduction such as bendability.Surface orientation coefficient can be located in range by MD multiplying power, heat-fixing temperature.In addition, conduct
Drawing process, successively biaxial drawing is more preferred than simultaneously biaxial drawing, enterprising in the direction TD after particularly preferably stretching in the MD direction
The successively biaxial drawing that row stretches.
In addition, the variation of the surface orientation coefficient for the width direction of the film after stretching of the invention, by its film
Overall width is divided into 10 equal portions and the difference of the maxima and minima of surface orientation coefficient that measures is preferably 0.02 or less, more preferably
It 0.015 or less, is most preferably 0.01 or less.When more than 0.02, mechanical characteristic has deviation, and in addition to this, the thickness of film is not
Equalization can become larger, and it is not preferable.In addition, in order to reduce the variation of the surface orientation coefficient, by the width for reducing non-stretched film
The difference in specific gravity (difference of crystallinity) in direction is realized.
In addition, the axis of orientation angle of the film after stretching of the invention is preferably in 0~40 degree of range.In the present invention
In, the orientation in the direction MD and the direction TD can equalize, but when more than 40 degree, film can deform after the heating, therefore unexcellent
Choosing.Therefore, identical as the curved method of common reduction as specific method, after TD stretching being carried out using reduction
The method of the contraction in the direction MD when heat fixation, but by reducing the central portion of non-stretched film and the crystallinity of end in casting
Difference, can reduce stretch after film end bending, be advantageous.
The lower limit of the puncture intensity of film of the invention is preferably 0.5N/ μm, more preferably 0.9N/ μm.Lower than 0.5N/ μm
When, intensity of the film in processing, when film is formed bag has deficiency.The upper limit of puncture intensity is preferably 1.5N/ μm, is more than
At 1.5N/ μm, improvement can be saturated.Puncture intensity can be located in range by MD multiplying power, heat-fixing temperature.
The lower limit of the impact strength (impact resistance) of film of the invention is preferably 0.05J/ μm, more preferably 0.06J/ μ
m.When lower than 0.05J/ μm, intensity has deficiency when using as bag.The upper limit of impact strength (impact resistance) is preferably 0.2J/
μm, when more than 0.2J/ μm, above-mentioned improvement can be saturated.
The lower limit of the hydroscopicity of film of the invention is preferably 0.1%, and when being lower than 0.1%, improvement can be saturated.Moisture absorption
The upper limit of rate is preferably 1%, when more than 1%, easily causes moisture absorption change in size etc..
The lower limit of the MD percent thermal shrinkage of film of the invention is preferably 0.1%, and when being lower than 0.1%, improvement can be saturated,
In addition to this, meeting mechanical property becomes fragile.The upper limit of MD percent thermal shrinkage is preferably 4%, when more than 4%, when due to the processing such as printing
Change in size can cause spacing deviation etc..
The lower limit of the TD percent thermal shrinkage of film of the invention is preferably 0.1%, and when being lower than 0.1%, improvement can be saturated,
In addition to this, meeting mechanical property becomes fragile.The upper limit of TD percent thermal shrinkage is preferably 3%, when more than 3%, when due to the processing such as printing
Change in size can cause the contraction etc. in the width direction of film.
The lower limit of the mist degree of film of the invention is preferably 0%.The upper limit of mist degree is preferably 50%, more preferably 30%,
Further preferably 20%.As long as not limited for the purposes of invisible content.It should be noted that mist degree is more than
When 30%, it can be difficult to see content when using as bag.
Laminated body passes through Gelbo torsion test obtained from film and sealant of the invention is laminated using dry lamination method
The lower limit for the pinhole number that (Gelbo Flex test) is generated is preferably 0.The upper limit of pinhole number is preferably 10, more preferably 5
It is a.When more than 10, film easily forms hole when using as bag.It is as be described hereinafter for the measuring method of pinhole number.
The application be based on filed on May 14th, 2012 Japanese Patent Application No. 2012-110536 opinion it is excellent
First weigh.The full content of Japanese Patent Application No. 2012-110536 specification is cited filed on May 14th, 2012
To the application as reference.
Embodiment
Then, the present invention is illustrated in further detail using embodiment, but the present invention is not limited to following examples.It needs
Illustrate, the evaluation of film is carried out by following measuring method.
[specific gravity of non-stretched film]
Various kinds is measured using Shimadzu Seisakusho Ltd.'s device for measuring specific gravity SGM-300P according to JIS Z8807 8 (weighing method in liquid)
Specific gravity of the product at 23 DEG C.
For the difference of width direction specific gravity, the sample of 10 points is taken in width direction from the non-stretched film obtained, is led to
Above method measurement specific gravity is crossed, the maximum value of the result of acquisition is subtracted into value obtained by minimum value divided by minimum value to acquire.
[mechanical characteristic (breaking strength, elongation at break)]
According to JIS K7113.The sample of width 10mm, length 100mm are cut out from film using razor.The sample that will be cut out
After being placed 12 hours under 23 DEG C, the atmosphere of 35%RH, under 23 DEG C, the atmosphere of 35%RH, with distance 40mm between chuck, stretch
Speed 200mm/ points of condition is measured, and uses the average value of 5 measurement results.Shimadzu Seisakusho Ltd. is used as measurement device
The AUTOGRAPH AG5000A of company's manufacture.
[planar orientation]
The sample of 10 points is taken in width direction from roller sample.About the sample, according to 5.1 (A of JISK7142-1996
Method), using sodium D-line as light source, utilize the refraction of refractive index (nx), width direction of Abbe refractometer measurement film length direction
Rate (ny), the refractive index (nz) of thickness direction, and it is calculate by the following formula surface orientation coefficient (Δ P).It should be noted that will obtain
Surface orientation coefficient average value as surface orientation coefficient.
Δ P=(nx+ny)/2-nz
The surface orientation coefficient difference of width direction is set as the difference of the maxima and minima of the sample of above-mentioned 10 points.
[axis of orientation angle]
The MOA-6004 type molecularly oriented meter manufactured using prince's tester Co., Ltd., acquires the strand of film end
It is orientated the angle of orientation (θ) of main shaft.
[impact strength]
Make manufactured impact tester using Toyo Co., Ltd.'s essence mechanism, measures under 23 DEG C of atmosphere, film pair
In the intensity of impact punching.Impact the substance that spherical surface uses 1/2 inch of diameter.Unit is J/ μm.
[puncture intensity]
" food, additive equal-specification benchmark the 3rd: utensil and container package " in based food health legislation (Showa 57 years
Health and human services department bulletin the 20th) " test method(s)s such as 2. intensity " measurement.By the needle of front end diameter 0.7mm to pierce through speed 50mm/
Minute pierces through film, and measurement needle runs through intensity when film, as puncture intensity.Measurement under room temperature (23 DEG C) into
Row, unit N.
[pinhole resistance]
By film and sealant (non-stretched propylene film of TOYOBO Co., LTD. manufacture, P1146, thickness of the invention
70 μm), using by 33.6 mass parts polyester polyol (Toyo-Morton, Ltd. manufacture, TM-509), 4.0 mass parts polyisocyanate cyanogen
The polyurethanes that acid esters (Toyo-Morton, Ltd. manufacture, CAT-10L) and 62.4 mass parts ethyl acetate are obtained by mixing
Adhesive carries out dry lamination, makes laminated body.
Above-mentioned laminated body is cut to the size of 20.3cm (8 inches) × 27.9cm (11 inches), by the length after the cutting
Square test film is modulated for placement 24 hours or more under conditions of 23 DEG C of temperature, relative humidity 50%
(conditioning).Then, which is rolled into the cylindrical shape of length 20.32cm (8 inches).Also, it will
One end of its cylindrical thin-film is fixed on Gelbo distortion tester (Rigaku Corporation manufacture, NO.901 type) (foundation
The specification of MIL-B-131C) discoid fixing head periphery, the other end of cylindrical thin-film is fixed on and is separated with fixing head
17.8cm (7 inches) and the periphery of the discoid moving head of opposite tester.Then, make moving head on the direction edge of fixing head
Parallel opposite both ends axis close to 440 ゜ are rotated during 7.6cm (3 inches), do not rotate then and the 6.4cm (2.5 that keeps straight on
Inch) after, these action reverseds are carried out, moving head is made to return to initial position, carry out bend test as 1 circulation,
With every 1 minute implement 40 circulation speed continuously repeatedly 1000 circulation.Implementation carries out at 5 DEG C.Then, removal is through testing
Film the periphery for being fixed on fixing head and moving head part, measure 17.8cm (7 inches) × 27.9cm (11 inches)
The pinhole number that interior part generates is (that is, measure every 497cm2The pinhole number of (77 square inches)).
[inherent viscosity of polyester]
So that 0.1g polyester is dissolved in phenol/tetrachloroethanes, (volumetric ratio: 25mL in the mixed solvent 3/2) makes at 30 DEG C
With the inherent viscosity of Ostwald viscosimeter measurement polyester.
[fusing point of polyester]
The differential scanning calorimeter (DSC) manufactured using SII Corporation, in sample size 10mg, heating rate
It is measured under 20 DEG C/min.Wherein, fusing point of the melting endotherm peak temperature that will test as polyester.
[thickness]
Utilize the thickness of the method measurement film according to JIS-Z-1702.
[percent thermal shrinkage]
150 DEG C of test temperature, 10 minutes heating times are set, in addition to this, is become using the size that JIS-C-2318 is recorded
Change test method determination percent thermal shrinkage.
[mist degree]
Using the method according to JIS-K-7105, using haze meter (NIPPON DENSHOKU INDUSTRIE Co.,
LTD. manufacture, NDH2000) sample is measured in the mist degree of 3 different positions, using its average value as mist degree.
[uniformity (Tv (%)) of thickness]
Diaphragm is cut out along longitudinal direction from the central portion of the film roll obtained, dial gauge is used with 5cm spacing
Measure film thickness, from its result calculate thickness uniformity.
[peel strength]
By film and sealant (non-stretched propylene film of TOYOBO Co., LTD. manufacture, P1146, thickness of the invention
70 μm), using by 33.6 mass parts polyester polyol (Toyo-Morton, Ltd. manufacture, TM-509), 4.0 mass parts polyisocyanate cyanogen
The polyurethanes that acid esters (Toyo-Morton, Ltd. manufacture, CAT-10L) and 62.4 mass parts ethyl acetate are obtained by mixing
Adhesive carries out dry lamination, makes laminated body.
Above-mentioned laminated body is cut to width 15mm, length 200mm as coupons, using Toyo Baldwin Co.,
LTD. " the Tension UMT-II-500 type " manufactured measures under conditions of 23 DEG C of temperature, relative humidity 65% in polyester
The peel strength on the joint surface in the untreated face and polyolefin resin interlayer of film.It should be noted that set tensile speed as
10cm/ minutes, peel angle be 180 degree.
[hydroscopicity]
Film of the invention is cut to the square of side length 50mm, utilizes the side according to JIS-K-7209-7.2.1 (A method)
Method, measurement are immersed in the weight change of the film before and after the water for keeping temperature to be 23 DEG C ± 2 DEG C.Hydroscopicity is calculated by following formula (1)
?.
Hydroscopicity (%)=100 × ([M2]-[M1])/[M1] (1)
It should be noted that [M1] is the film weight before immersion in above-mentioned formula (1), [M2] is the film weight after immersion
Amount.
[embodiment 1]
Using twin screw vented extruders, addition containing PBT resin (Mitsubishi Engineering-Plastics manufacture NOVADURAN5020,
220 DEG C of fusing point) and the calcium carbonate as lubricant masterbatch, with blend together lubricant concentration be 2000ppm, obtained material is existed
It melting at 270 DEG C, the T- mold from 270 DEG C is cast later, the chill roll for making it be sealed at 0 DEG C using the closely sealed method of electrostatic,
Obtain non-stretched film.For the surface temperature of chill roll, (thermocouple) is measured with the interval 10cm in width direction, as a result
Its deviation is 3 DEG C or less.Then, 3.2 times of roller stretchings are carried out along longitudinal direction at 60 DEG C, secondly, using stenter at 80 DEG C
3 times of stretchings are carried out along transverse direction, after implementing nervous heat treatment in 3 seconds and the processing of mitigation in 1 second at 200 DEG C, cuts off and removes both ends
Portion is to obtain the PBT film with a thickness of 12 μm.By the film forming condition of the film of acquisition, physical property and evaluation result is shown in table 1.
It should be noted that the axis of orientation angle of film end is 35 degree, the deformation of the sample after percent thermal shrinkage measurement is small.
[embodiment 2]
Using twin screw vented extruders, addition contains PBT resin (Mitsubishi Engineering-Plastics manufacture NOVADURAN5020)
With the masterbatch of the calcium carbonate as lubricant, it is 2000ppm with lubricant concentration is blended together, obtained material is melted at 270 DEG C,
Melt line is directed into the static mixer (STMX) of 12 elements later.Segmentation/the stacking for carrying out PBT molten mass as a result, is obtained
Obtain the multilayered molten body formed by identical raw material.Later, it is directed into 270 DEG C of T- mold and casts, it is close using electrostatic
The legal chill roll for making it be sealed at 15 DEG C obtains non-stretched film.For the surface temperature of chill roll, width direction with
The interval 10cm is measured (thermocouple), and as a result its deviation is 3 DEG C or less.Then, 3.8 times of rollers are carried out along longitudinal direction at 60 DEG C
It stretches, secondly, carrying out 3 times of stretchings along transverse direction at 65 DEG C using stenter, implements nervous heat treatment in 3 seconds at 200 DEG C
After mitigation processing in 1 second, cuts off and remove both ends to obtain the PBT film with a thickness of 12 μm.By the film of acquisition
Film forming condition, physical property and evaluation result is shown in table 1.It should be noted that the axis of orientation angle of film end is 25 degree, heat is received
The deformation of sample after shrinkage measurement is small.
[embodiment 3~4]
Film is obtained by the condition that table 1 is recorded.The film forming condition of the film of acquisition, physical property and evaluation result are shown in
Table 1.It should be noted that poly- (the adipic acid butanediol that Ecoflex (logging in trade mark) has used BASF JAPAN LTD. to manufacture
Ester-co- mutual-phenenyl two acid bromide two alcohol ester) copolymer (PBAT).
[table 1]
[comparative example 1]
Chill-roll temperature when casting is set as 15 DEG C, in addition to this, with the means discussion filming of the record of embodiment 1.
Film forming condition is shown in table 2.Non-stretched film is broken when MD is stretched, and fails to obtain film.
[comparative example 2]
Film is obtained by the condition that table 2 is recorded.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 for the condition acquisition recorded by table 2 as sample.It is adjusted in a manner of with a thickness of 20 μm
Winding speed manufactures film.It should be noted that the axis of orientation angle of film end is 5 degree hereinafter, after percent thermal shrinkage measurement
Sample do not observe deformation.
[comparative example 4]
Using TOYOBO Co., it is (thick that ester (TOYOBO ESTER) (registered trademark) film E5100 spins in Japan of LTD. manufacture
12 μm of degree).
[reference example 1]
As representative PBT film, the PBT film manufactured using commercially available Kansai Chemicals Co., Ltd..
The axis of orientation angle of film end is 5 degree hereinafter, the sample after percent thermal shrinkage measurement does not observe deformation.
[table 2]
Industrial availability
For polyester film of the invention, caused fracture, especially logical when stretching for the PBT for inhibiting crystallization rate big
It crosses caused by the difference for inhibiting the cooling velocity in shear velocity, the casting for the molten resin that width direction is discharged from mold and ties
Brilliant degree unevenness homogenizes, reduce unstretched state when width direction difference in specific gravity, thus, it is possible to significantly inhibit stretch when fracture.
The present invention can industrially be implemented, and can improve harmony, the impact resistance etc. in the mechanical characteristic in the direction MD and TD.
Claims (3)
- It is thin for the biaxially stretched polyester that is stretched to non-stretched film 1. a kind of manufacturing method of Biaxially oriented polyester film The manufacturing method of film, the non-stretched film are to carry out the raw material of same composition obtained from multiple stratification cast again,The raw material is the polyester resin that the containing ratio of polybutylene terephthalate (PBT) is 60 mass % or more,The multiple stratification uses only one extruder and the multilayer device for importeding into extruder to the melt line between mold It carries out, is 8 layers or more by the number of plies that multiple stratification is formed.
- It is thin for the biaxially stretched polyester that is stretched to non-stretched film 2. a kind of manufacturing method of Biaxially oriented polyester film The manufacturing method of film, the non-stretched film are to carry out the raw material of same composition obtained from multiple stratification cast again,The raw material is the polyester resin that the containing ratio of polybutylene terephthalate (PBT) is 60 mass % or more,The multiple stratification using two or more extruder and imported into extruder to the melt line between mold multilayer disguise The raw material for the same composition to carry out, sent out from each extruder is set in the quality % of each raw material of compounding, biggest quality % Difference with minimum mass % be 10 mass % hereinafter, and the polyester resin of compounding when being copolymer, the maximum of the monomer of copolymerization is rubbed The difference of your % and minimum mole % is 5 moles of % hereinafter, being 8 layers or more by the number of plies that multiple stratification is formed.
- 3. the manufacturing method of Biaxially oriented polyester film according to claim 1 or 2, wherein the non-stretched film It is stretched as successively biaxial drawing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012-110536 | 2012-05-14 | ||
| JP2012110536 | 2012-05-14 | ||
| CN201380025562.5A CN104321372B (en) | 2012-05-14 | 2013-05-07 | Polyester film and its manufacturing method |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380025562.5A Division CN104321372B (en) | 2012-05-14 | 2013-05-07 | Polyester film and its manufacturing method |
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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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| CN201380025562.5A Active CN104321372B (en) | 2012-05-14 | 2013-05-07 | Polyester film and its manufacturing method |
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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) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY172893A (en) * | 2012-05-14 | 2019-12-13 | Toyo Boseki | Polyester film and method for producing same |
| WO2014077197A1 (en) * | 2012-11-16 | 2014-05-22 | 東洋紡株式会社 | Biaxially oriented polyester film and method for producing same |
| KR102090124B1 (en) * | 2013-11-13 | 2020-03-17 | 도요보 가부시키가이샤 | Biaxially stretched polybutylene terephthalate film |
| US20170088682A1 (en) * | 2014-05-21 | 2017-03-30 | Toyobo Co., Ltd. | Biaxially stretched polybutylene terephthalate film, manufacturing method therefor, and gas barrier laminate film |
| JP6242299B2 (en) * | 2014-06-19 | 2017-12-06 | 株式会社クラレ | Method for measuring puncture strength of stretched film |
| JP6327222B2 (en) * | 2014-09-30 | 2018-05-23 | 住友化学株式会社 | Polarizing plate, polarizing plate with adhesive, and liquid crystal display device |
| JP6588720B2 (en) * | 2015-03-31 | 2019-10-09 | 興人フィルム＆ケミカルズ株式会社 | Easy tear biaxially stretched polybutylene terephthalate film |
| JP6874277B2 (en) * | 2015-04-24 | 2021-05-19 | 東洋紡株式会社 | Biaxially stretched polyester film and its manufacturing method |
| CN107531015A (en) | 2015-04-24 | 2018-01-02 | 东洋纺株式会社 | Biaxially oriented polyester film and its manufacture method |
| WO2016171172A1 (en) | 2015-04-24 | 2016-10-27 | 東洋紡株式会社 | Biaxially stretched polyester film, and production method therefor |
| ES2828040T3 (en) * | 2015-08-19 | 2021-05-25 | Toyo Boseki | Heat Shrinkable Polyester Film and Container |
| US20200326027A1 (en) * | 2016-03-30 | 2020-10-15 | Toyobo Co., Ltd. | Laminate for vacuum insulation material |
| JP6769083B2 (en) * | 2016-04-19 | 2020-10-14 | 東洋紡株式会社 | How to manufacture ceramic capacitors |
| WO2018062329A1 (en) * | 2016-09-30 | 2018-04-05 | 大日本印刷株式会社 | Film and film production method, and packaging material equipped with film |
| JP6947052B2 (en) * | 2017-01-23 | 2021-10-13 | 三菱ケミカル株式会社 | Polyester multilayer film |
| WO2018179726A1 (en) * | 2017-03-28 | 2018-10-04 | 東洋紡株式会社 | Biaxially oriented polyester film and method for manufacturing same |
| JP7056175B2 (en) * | 2017-03-29 | 2022-04-19 | 大日本印刷株式会社 | Laminated body and bag composed of the laminated body |
| JP7056174B2 (en) * | 2017-03-29 | 2022-04-19 | 大日本印刷株式会社 | Laminated body and bag composed of the laminated body |
| CN110691808A (en) * | 2017-06-06 | 2020-01-14 | 东洋纺株式会社 | Biaxially oriented polyester film |
| JP2019171587A (en) * | 2018-03-27 | 2019-10-10 | 東洋紡株式会社 | Polyester film and gas barrier laminate film |
| WO2019187694A1 (en) * | 2018-03-30 | 2019-10-03 | 東洋紡株式会社 | Polyester film roll |
| JP7024645B2 (en) * | 2018-07-20 | 2022-02-24 | 東洋紡株式会社 | Polyester film roll |
| TW202012191A (en) * | 2018-08-08 | 2020-04-01 | 日商東洋紡股份有限公司 | Gas barrier laminate film and the method thereof, laminating body, packaging bag |
| TWI803697B (en) * | 2018-10-05 | 2023-06-01 | 日商東洋紡股份有限公司 | Biaxially oriented polyamide film and roll of polyamide film |
| WO2020175067A1 (en) * | 2019-02-26 | 2020-09-03 | 東洋紡株式会社 | Biaxially oriented polyester film, and production method for biaxially oriented polyester film |
| WO2020175058A1 (en) * | 2019-02-26 | 2020-09-03 | 東洋紡株式会社 | Biaxially oriented polyester film, and production method for biaxially oriented polyester film |
| JP7365569B2 (en) | 2019-02-26 | 2023-10-20 | 東洋紡株式会社 | Biaxially oriented polyester film and method for producing biaxially oriented polyester film |
| DK3953141T3 (en) * | 2019-04-11 | 2023-05-08 | Basf Se | PROCEDURE FOR THERMOFORMING OF POLYBUTYLENE TEREPHTHALATE |
| KR102567191B1 (en) | 2021-04-05 | 2023-08-14 | 도레이첨단소재 주식회사 | Copolymeric polyester film and pouch case for secondary battery and pouch-type secondary battery using the same |
| AT525673B1 (en) * | 2022-03-25 | 2023-06-15 | Florian Bamberger | Process for making thermoformed plastic parts from polyethylene terephthalate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0216029A (en) * | 1988-07-04 | 1990-01-19 | Unitika Ltd | Polyester biaxially oriented film |
| CN1213340A (en) * | 1996-03-08 | 1999-04-07 | 美国3M公司 | Multiplayer polyester film |
| JP4273855B2 (en) * | 2002-08-08 | 2009-06-03 | 東レ株式会社 | Laminated film and packaging 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 |
| JPH05200860A (en) * | 1992-01-29 | 1993-08-10 | Okura Ind Co Ltd | Heat-resistant bag |
| 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 |
| WO1998013414A1 (en) * | 1996-09-24 | 1998-04-02 | 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 |
| JP3680833B2 (en) * | 2002-01-11 | 2005-08-10 | 東洋紡績株式会社 | Production method of polyester film |
| JP3709869B2 (en) * | 2002-01-11 | 2005-10-26 | 東洋紡績株式会社 | Polyester film |
| KR101011290B1 (en) * | 2002-09-10 | 2011-01-28 | 도레이 카부시키가이샤 | 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 |
| JP4257619B2 (en) * | 2007-01-31 | 2009-04-22 | 東洋紡績株式会社 | Surface light diffusing 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 |
| MY172893A (en) * | 2012-05-14 | 2019-12-13 | Toyo Boseki | Polyester film and method for producing same |
| WO2014077197A1 (en) * | 2012-11-16 | 2014-05-22 | 東洋紡株式会社 | Biaxially oriented polyester film and method for producing same |
-
2013
- 2013-05-07 MY MYPI2014703346A patent/MY172893A/en unknown
- 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 KR KR1020147031598A patent/KR101961002B1/en active IP Right Grant
- 2013-05-07 CN CN201810810311.2A patent/CN109111585A/en not_active Withdrawn
- 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 |
| CN1213340A (en) * | 1996-03-08 | 1999-04-07 | 美国3M公司 | Multiplayer polyester film |
| JP4273855B2 (en) * | 2002-08-08 | 2009-06-03 | 東レ株式会社 | Laminated film and packaging film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013256110A (en) | 2013-12-26 |
| JP6194629B2 (en) | 2017-09-13 |
| KR101961002B1 (en) | 2019-03-21 |
| MY172893A (en) | 2019-12-13 |
| CN104321372A (en) | 2015-01-28 |
| JP2016172454A (en) | 2016-09-29 |
| TWI622608B (en) | 2018-05-01 |
| KR20150008872A (en) | 2015-01-23 |
| JP6202146B2 (en) | 2017-09-27 |
| CN104321372B (en) | 2018-07-06 |
| WO2013172214A1 (en) | 2013-11-21 |
| TW201406831A (en) | 2014-02-16 |
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