CN104321372B - Polyester film and its manufacturing method - Google Patents
Polyester film and its manufacturing method Download PDFInfo
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- CN104321372B CN104321372B CN201380025562.5A CN201380025562A CN104321372B CN 104321372 B CN104321372 B CN 104321372B CN 201380025562 A CN201380025562 A CN 201380025562A CN 104321372 B CN104321372 B CN 104321372B
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- film
- pbt
- polybutylene terephthalate
- biaxial stretch
- stretching
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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
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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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- 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
Offer can industrially be implemented, and the polyester film that the harmony of the mechanical characteristic on MD and TD directions, impact resistance etc. are excellent.A kind of polyester film, it is formed by the polyester resin comprising 60 mass % more than polybutylene terephthalate (PBT)s, 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, impact strength is 0.05J/ μm or more and puncture intensity is 0.5N/ μm or more.
Description
Technical field
The present invention relates to polyester film and its manufacturing methods.Systems suitable for using nylon film at present
Or the harmonious excellent polyester film and its system of other soft the purposes of film, impact resistance, bendability, mechanical strength
Make method.
Background technology
The mechanical characteristic of polybutylene terephthalate (PBT) (PBT), excellent impact resistance, therefore it is used as engineering plastics so far
It uses, particularly also serves as useful materials'use from the aspect of crystallization rate is 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 crystallization, cause to stretch difficult.Relative to
This, in order to play the PBT characteristics that have 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 films are not still to 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 films obtained using inflation method, since its manufacturing method causes to stretch again
Rate be difficult to uniformly, there are thickness and precision it is bad the problem of, it is also low there are puncture intensity and then since surface orientation coefficient can not increase
The problems such as.Therefore, the PBT films obtained to the biaxial stretching process carried out using stenter are studied.Hereinafter, for the past
The research of PBT films carry out some discussion.
At present it is known that there is following technology：After being pulled up in a manner of stretching ratio is made to be less than 3.5 times in TD side, with
The deformation velocity of more than 100000%/min stretches to manufacture biaxial stretch-formed PBT films in the MD direction, so as to manufacture uniform drawing
The technology for the film without uneven thickness stretched (for example, see patent document 1).However, knot of the prior art from embodiment
Fruit understands that there are the following problems：Due to only accelerating the deformation velocity in MD directions, elongation can be low, can not become in MD directions and TD
Direction obtains balanced film.
Furthermore it is known that there is following technology：Based on experimental result, by it is non-stretched when crystallinity calculate draft temperature, herein
After the stretching for more than temperature implementing MD (or TD) direction 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 (such as is joined when thus manufacturing uneven thickness, film
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, thus there are the mechanical characteristic in MD directions and TD directions harmony it is bad the problem of.
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 PBT are formed is laminated in the prior art, therefore as 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 a feature for the PBT films for playing script, and the resin composition in film is two kind, cutting chip during therefore, it is difficult to be film-made
Recycled etc. being again added in raw material, there are economic aspect it is unfavorable the problem of.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 51-146572 bulletins
Patent document 2：Japanese Unexamined Patent Application 51-40904 bulletins
Patent document 3：No. 4273855 bulletins of Japanese Patent No.
Invention content
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 fractures when stretching, the melting discharged especially by inhibition in width direction from mold
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, MD/TD directions
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 60 mass % more thans PBT, MD's is disconnected
Split that elongation is more than 80%, the elongation at break of TD is more than 80%, 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, the cooling of the shear velocity of molten resin, Jiao Zhu Time discharged especially by inhibition in width direction 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 the film to stretch, can industrially implement, and can improve the mechanical characteristic in MD and TD directions
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
Upper, further preferably more than 70 mass %, particularly preferably more than 75 mass %, it is most preferably more than 80 mass %.It is less than
During 60 mass %, the impact strength and pinhole resistance of film reduce, and film characteristics are simultaneously insufficient.
For as PBT used in main composition, as dicarboxylic acid component, terephthalic acid (TPA) for 90 moles of % with
On be it is preferred, more preferably 95 moles of more than %, further preferably 98 moles of more than %, be most preferably 100 moles of %.Make
For glycol component, 1,4-butanediol is preferred, more preferably 95 moles of more than %, further preferably for 90 moles of more than %
For 97 moles of more than %, do not include most preferably when polymerizeing by the substance other than the by-product of the ehter bond of 1,4- butanediols generation.
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- pentanediols, 1,6-HD, diethylene glycol, hexamethylene two
Alcohol, polyethylene glycol, polytetramethylene glycol, polycarbonate glycol etc..
These need can meet and it is aftermentioned others 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) when, other polyester resin, as additive, be bent for improving when pinhole resistance and make soft
Any one of soft polyether components, polycarbonate component, polyester component Polyester obtained from copolymerization and polyamide-based bullet
Property body.
The lower limit of the additive amount of these additives is preferably 0 mass %, and the upper limit is preferably 20 mass %.During more than 20%,
In addition to this said effect saturation, can cause transparency reduction of film etc..
The lower limit of resin melt temperature is preferably 200 DEG C, and during less 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.
Aforementioned polyester resin can contain currently known additive, such as lubricant, stabilizer, coloring as needed
Agent, antioxidant, antistatic agent, ultra-violet absorber etc..
As lubricant type, preferably inorganic system's lubrication material such as organic lubricant, silica, calcium carbonate, aluminium oxide
Material, more preferable silica, calcium carbonate, particularly preferred calcium carbonate.Thus, it is possible to embody the transparency and sliding of film.
The lower limit of lubricant concentration is preferably 100ppm, and during less than 100ppm, the sliding of film can reduce.Lubricant is dense
The upper limit of degree is preferably 20000ppm, and during more than 20000ppm, the transparency of film can reduce.
As for obtaining the key of 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 cool down not with
The face of chill roll contact may also set up contact roller to improve cooling efficiency.
In addition, as other methods, the inventors of the present invention have found：It can be reduced by using aftermentioned novel method and do not drawn
The crystallinity for stretching the width direction of film is poor.I.e., it was found that in casting by the way that the raw material multiple stratification of same composition is carried out again
Casting can reduce the difference of the crystallinity of the width direction of non-stretched film, and tensile stress when can stretch TD is evenly distributed.Mesh
Before, in casting, the crystallinity of the end of non-stretched film increases, and the crystallinity of the central portion of non-stretched film is lower, therefore
Become uneven in width direction of the tensile stress in non-stretched film when TD directions stretch, so as to which film is easily broken off, because
This, needs to carry out TD stretchings at higher temperatures.In contrast, although the reason is to speculate, even in by same resin layers
There is also the interfaces of layer when folded, crystallize and accelerate 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 use commonly
Multilayer device (multilayer supply head, static mixer, multilayer branch manifold etc.), such as will never using the extruder of two or more
Method for being laminated for multilayer using supply head, static mixer, multi-manifold etc. with the thermoplastic resin that flow path is sent out etc..It needs
It is noted that when by the raw material multiple stratification of same composition, an extruder can be used only, above-mentioned multilayer device is led
Enter to extruder to the melt line (melt line) between mold, thus reach the purpose of the present invention.
It should be noted that the raw material of same composition refers to, when using the extruder of two or more, set from each extrusion
In the content of each raw material being compounded in the thermoplastic resin that machine is sent out, the difference of biggest quality % and minimum mass % allows for 10
Below quality %, it is further below 5 mass %, specifically for below 2 mass %.When polyester uses copolymer, set from each and squeeze
Go out in the content of the monomer of copolymerization being compounded in the thermoplastic resin of machine submitting, maximum mole % and the difference of minimum mole % are allowed
For 5 moles of below %, be further 3 moles of below %, specifically for 2 moles of below %.In addition, the molecular weight of each raw material also may be used
With difference, but by GPC acquire styrene conversion weight average molecular weight when, with the big substance of the difference divided by molecular weight of its molecular weight
Molecular weight value be preferably less than 30%, as long as further preferably less than 20%, 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.
It should be noted that above-mentioned multilayer device is imported into extruder to melting between mold using only an extruder
Melt the method for pipeline, the management aspect of simplicity, each raw material from device considers to be also preferred method.
The lower limit of mold temperature is preferably 200 DEG C, and during less 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, during more than 350 DEG C, in addition to the thickness of film become it is uneven 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, during less 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 during more than 80 DEG C, the crystallinity of non-stretched film becomes
It is excessively high to become difficult so as to stretch.In order to reduce the difference of the crystallinity of the width direction of non-stretched film, it is to have to reduce crystallinity
Effect, from this viewpoint, without using aftermentioned multiple stratification when method when, chill-roll temperature is preferably less than 10 DEG C, into
One step is less than 5 DEG C.At this point, condensing in order to prevent, the ambient humidity near chill roll is preferably reduced.On the other hand, Ke Yitong
It crosses using poor to reduce the crystallinity of the width direction of non-stretched film the methods of aftermentioned multiple stratification, 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 less than 5 DEG C, 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, cause to cool down the temperature rise of roller surface due to the resin of surface contact high temperature.In general, chill roll
Cooling water is circulated so as to be cooled down by piping in inside, but is the need to ensure that sufficient cooling water inflow, designs matching for piping
It puts, repair so as to not have to adhere to sludge etc. in piping to reduce the temperature difference of the width direction of cooling roller surface.Especially
Be be not used multiple stratification when method and while cooling down at low temperature, needs to pay attention to.
During the casting of multilayered structure, at least 3 layers or more, preferably more than 5 layers, 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 stablized, it may have appearance investigation and other effects, therefore it is preferred that.
Then drawing process is illustrated.Can may be double successively for simultaneously biaxial drawing for drawing process
Axis stretches, but for the puncture intensity for improving 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 temperatures is preferably 40 DEG C, more preferably 45 DEG C.During less 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.During more than 100 DEG C, lead to the power of film when being difficult to be orientated sometimes
Learning characteristic reduces.
The lower limit of MD stretching ratios is preferably 2.5 times, during less than 2.5, leads to the mechanics of film when being difficult to be orientated sometimes
Characteristic, uneven thickness deteriorate.The upper limit of MD stretching ratios is preferably 5 times, during more than 5 times, improves mechanical strength, the thickness of film
Uneven effect can saturation.
The lower limit of TD draft temperatures is preferably 40 DEG C, during less than 40 DEG C, easily causes the fracture of film.TD draft temperatures
The upper limit is preferably 100 DEG C, during more than 100 DEG C, the mechanical characteristic of film is caused to reduce when being difficult to be orientated sometimes.
The lower limit of TD stretching ratios is preferably 2.5 times, during less than 2.5 times, cause when being difficult to be orientated sometimes mechanical characteristic,
Uneven thickness deteriorates.The upper limit of TD stretching ratios is preferably 5 times, during more than 5 times, improves mechanical strength, the uneven thickness of film
Effect can saturation.
The lower limit of TD heat-fixing temperatures is preferably 150 DEG C, and during less than 150 DEG C, the percent thermal shrinkage of film becomes larger, and causes processing
When offset, shrink.The upper limit of TD heat-fixing temperatures is preferably 250 DEG C, during 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 rates is preferably 0.5%, and during less than 0.5%, the fracture of film is easily caused in heat fixation.TD
The upper limit of relaxation rate is preferably 10%, and during more than 10%, film generates relaxation etc. so as to which uneven thickness occur.
For the present 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 during less than 3 μm.The upper limit of film thickness is preferably 100 μm, is more preferably
75 μm, further preferably 50 μm.During 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.During more than 25%, can generate roller bad order,
Caused deformation etc. during secondary operation, it is not preferable.In order to reduce the difference of maximum gauge and minimum thickness in overall width, need
The stretching ratio for making width direction is uniform, and crystallinity during therefore, it is necessary to make non-stretched in advance is uniform.
The lower limit of the proportion of the central portion of the non-stretched film of the present invention is preferably 1.25g/cm3, less than 1.25g/cm3When,
The effect for improving the draftability of non-stretched film can saturation.The upper limit of the proportion 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 proportion of the non-stretched film of the present invention is preferably 0.03g/cm3, more than 0.03g/
cm3When, the tensile stress of width direction is uneven, fracture so as to cause film, cause film width direction stretching not
, become uneven thickness, the reason of physical property is uneven.
The lower limit of MD elasticity modulus of the film of the present invention is preferably 1GPa, and during less than 1GPa, film easily extends, and is printing
Brush, lamination can cause spacing (pitch) offset etc. when processing.The upper limit of MD elasticity modulus is preferably 2GPa, during more than 2GPa,
After film and various sealants etc. are bonded, it is unfavorable to be had in terms of the processabilities such as drawing process.
The lower limit of TD elasticity modulus of the film of the present invention is preferably 1GPa, and during less than 1GPa, film easily extends, and is adding
Working hour can cause problem.The upper limit of TD elasticity modulus is preferably 2GPa, and during more than 2GPa, film and various sealants etc. are bonded
Afterwards, it is unfavorable to be had 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 the range of.
The lower limit of TD fracture strengths of the film of the present invention is preferably 100MPa, during less than 100MPa, during the processing of film
Fracture etc. can be caused.The upper limit of TD fracture strengths is preferably 500MPa, during more than 500MPa, improves the effect of the fracture strength of film
Fruit can saturation.
The lower limit of the MD elongation at breaks of the film of the present invention is preferably 80%, more preferably 90%.It is thin during less than 80%
After film and various sealants etc. are bonded, it is unfavorable to be had in terms of the processabilities such as drawing process.The upper limit of MD elongation at breaks does not have
Special limitation, preferably 200%.In the range of MD elongation at breaks can be located at by MD multiplying powers, heat-fixing temperature.
The lower limit of the TD elongation at breaks of the film of the present invention is preferably 80%, more preferably 90%.It is thin during less than 80%
After film and various sealants etc. are bonded, it is unfavorable to be had in terms of the processabilities such as drawing process.The upper limit of TD elongation at breaks does not have
Special limitation, preferably 500%.In the range of TD elongation at breaks can be located at by TD multiplying powers, heat-fixing temperature.
The lower limit of surface orientation coefficient of the film of the present invention is preferably 0.12, during less than 0.12, puncture intensity, impact strength
Etc. can reduce.The upper limit of surface orientation coefficient is preferably 0.14, and during more than 0.14, the productivity of film reduces, in addition to this, sometimes
It can observe the reductions such as bendability.In the range of surface orientation coefficient can be located at by MD multiplying powers, heat-fixing temperature.In addition, conduct
Drawing process, successively biaxial drawing is more preferred than simultaneously biaxial drawing, enterprising in TD directions 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 the stretching of the present invention, by its film
The difference of the maxima and minima of surface orientation coefficient that overall width is divided into 10 equal portions and measures is preferably less than 0.02, is more preferably
Less than 0.015, it is most preferably less than 0.01.During 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 the stretching of the present invention is preferably in 0~40 degree of range.In the present invention
In, the orientation in MD directions and TD directions can equalize, but during more than 40 degree, and film can deform after the heating, therefore unexcellent
Choosing.Therefore, it is identical with the method for common reduction bending as specific method, after reduction progress TD stretchings may be used
The method of the contraction in MD directions during 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 the film of the present invention is preferably 0.5N/ μm, more preferably 0.9N/ μm.Less than 0.5N/ μm
When, film processing when, by film formed bag when intensity have deficiency.The upper limit of puncture intensity is preferably 1.5N/ μm, is more than
At 1.5N/ μm, improvement can saturation.In the range of puncture intensity can be located at by MD multiplying powers, heat-fixing temperature.
The lower limit of the impact strength (impact resistance) of the film of the present invention is preferably 0.05J/ μm, more preferably 0.06J/ μ
m.During less than 0.05J/ μm, intensity has deficiency when being used as bag.The upper limit of impact strength (impact resistance) is preferably 0.2J/
μm, during more than 0.2J/ μm, above-mentioned improvement can saturation.
The lower limit of hydroscopicity of the film of the present invention is preferably 0.1%, and during less than 0.1%, improvement can saturation.Moisture absorption
The upper limit of rate is preferably 1%, during more than 1%, easily causes moisture absorption change in size etc..
The lower limit of MD percent thermal shrinkages of the film of the present invention is preferably 0.1%, during less than 0.1%, improvement can saturation,
In addition to this, meeting mechanical property becomes fragile.The upper limit of MD percent thermal shrinkages is preferably 4%, during more than 4%, due to printing when processing
Change in size can cause spacing deviation etc..
The lower limit of TD percent thermal shrinkages of the film of the present invention is preferably 0.1%, during less than 0.1%, improvement can saturation,
In addition to this, meeting mechanical property becomes fragile.The upper limit of TD percent thermal shrinkages is preferably 3%, during more than 3%, due to printing when processing
Change in size can cause contraction in the width direction of film etc..
The lower limit of the mist degree of the film of the present invention is preferably 0%.The upper limit of mist degree is preferably 50%, more preferably 30%,
Further preferably 20%.As long as the purposes not see content, just not limited.It should be noted that mist degree is more than
It can be difficult to see content when 30%, when using as bag.
Laminated body passes through Gelbo torsion tests obtained from the film and sealant of the present invention is laminated in 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, is more preferably 5
It is a.During more than 10, film easily forms hole when being used as bag.For pinhole number assay method as be described hereinafter.
The application is based on the excellent of No. 2012-110536 opinion of Japanese Patent Application No. filed in 14 days Mays in 2012
First weigh.The full content of the specification of Japanese Patent Application No. filed in 14 days Mays in 2012 2012-110536 is cited
To the application as reference.
Embodiment
Then, the present invention is illustrated, but the present invention is not limited to following examples in further detail using embodiment.It needs
Illustrate, the evaluation of film is carried out by following measuring method.
[proportion of non-stretched film]
According to JIS Z8807 8 (weighing method in liquid) various kinds is measured using Shimadzu Seisakusho Ltd. device for measuring specific gravity SGM-300P
Proportion of the product at 23 DEG C.
For the difference of width direction proportion, the sample of 10 points is taken in width direction from the non-stretched film obtained, is led to
It crosses the above method and measures proportion, value obtained by the maximum value of the result of acquisition is subtracted minimum value divided by minimum value to acquire.
[mechanical characteristic (fracture 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, the distance 40mm between chuck, stretch
The condition that 200mm/ points of speed 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, the refraction of refractive index (nx), width direction of film length direction are measured using Abbe refractometer
Rate (ny), the refractive index (nz) of thickness direction, and surface orientation coefficient (Δ P) is calculated by following formula.It should be noted that it 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 meters manufactured using prince's tester Co., Ltd. acquire 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, measure 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 in based food health legislation:Utensil and container package " (Showa 57 years
Health and human services department bulletin the 20th) " test method(s)s such as 2. intensity " measure.By the needle of front end diameter 0.7mm to pierce through speed 50mm/
Minute pierces through film, intensity when needle runs through film is measured, as puncture intensity.Measure under room temperature (23 DEG C) into
Row, unit N.
[pinhole resistance]
By film and sealant (non-stretched propylene film of TOYOBO Co., LTD. manufactures, P1146, the thickness of the present 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), the length after this is cut off
Square test film is placed 24 hours or more and is modulated 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).It also, will
One end of its cylindrical thin-film is fixed on Gelbo distortion testers (Rigaku Corporation manufactures, NO.901 types) (foundation
The specification of MIL-B-131C) discoid gland periphery, the other end of cylindrical thin-film is fixed on and is separated with gland
The periphery of 17.8cm (7 inches) and the discoid moving head of opposite tester.Then, make moving head on the direction edge of gland
The axis at parallel opposite both ends close to 440 ゜ are rotated during 7.6cm (3 inches), is not rotated 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, bend test is carried out as 1 cycle,
With every 1 minute implement 40 cycle speed continuously repeatedly 1000 cycle.Implementation carries out at 5 DEG C.Then, it removes through experiment
Film the periphery for being fixed on gland and moving head part, measure 17.8cm (7 inches) × 27.9cm (11 inches)
The pinhole number that interior part generates is (that is, measure per 497cm2The pinhole number of (77 square inches)).
[inherent viscosity of polyester]
0.1g polyester is made to be dissolved in phenol/tetrachloroethanes (volumetric ratio：3/2) 25mL in the mixed solvents, make at 30 DEG C
The inherent viscosity of polyester is measured with Ostwald viscosimeters.
[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 endotherm peak temperature as polyester is melted using what is detected.
[thickness]
The thickness of film is measured using the method 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) mist degree of the sample in 3 different positions is measured, 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. manufactures, P1146, the thickness of the present 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 types " manufactured, under conditions of 23 DEG C of temperature, relative humidity 65%, measures in polyester
The untreated face of film and the peel strength on the composition surface of vistanex interlayer.It should be noted that set tensile speed as
10cm/ minutes, peel angle be 180 degree.
[hydroscopicity]
The film of the present invention is cut to the square of length of side 50mm, utilizes the side according to JIS-K-7209-7.2.1 (A methods)
Method measures and is immersed in the weight change for keeping temperature for the film before and after 23 DEG C ± 2 DEG C of water.Hydroscopicity is calculated by following formula (1)
.
Hydroscopicity (%)=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
Amount.
[embodiment 1]
Using twin screw vented extruders, addition containing PBT resin (Mitsubishi Engineering-Plastics manufacture NOVADURAN5020,
220 DEG C of fusing point) and calcium carbonate as lubricant masterbatch, with lubricant concentration is blended together for 2000ppm, obtained material is existed
It melting at 270 DEG C, the T- molds from 270 DEG C are cast later, it are made to be sealed at 0 DEG C of chill roll using the closely sealed method of electrostatic,
Obtain non-stretched film.For the surface temperature of chill roll, (thermocouple) is measured with 10cm intervals in width direction, as a result
Its deviation is less than 3 DEG C.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 so as to obtain the PBT films that thickness is 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 17 degree, the deformation of the sample after percent thermal shrinkage measure 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, with lubricant concentration is blended together for 2000ppm, obtained material is melted at 270 DEG C,
Melt line is directed into the static mixer (STMX) of 12 elements later.Segmentation/stacking of PBT molten masses is carried out as a result, is obtained
Obtain the multilayered molten body formed by identical raw material.Later, 270 DEG C of T- molds are directed into and are cast, it is close using electrostatic
It is legal that it is made to be sealed at 15 DEG C of chill roll, obtain non-stretched film.For the surface temperature of chill roll, width direction with
10cm intervals are measured (thermocouple), and as a result its deviation is less than 3 DEG C.Then, 3.8 times of rollers are carried out along longitudinal direction at 60 DEG C
It stretches, secondly, carries out 3 times of stretchings along transverse direction at 65 DEG C using stenter, implement the nervous heat treatment of 3 seconds at 200 DEG C
After the mitigation processing of 1 second, cut off and remove both ends so as to obtain the PBT films that thickness is 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 15 degree, heat is received
The deformation of sample after shrinkage measure 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 Ecoflex (logging in quotient Standard) has used poly- (the adipic acid butanediol that BASF JAPAN LTD. are manufactured
Ester-co- mutual-phenenyl two acid bromide two alcohol esters) copolymer (PBAT).
[table 1]
[comparative example 1]
Chill-roll temperature when casting is set as 15 DEG C, in addition to this, the means discussion filming recorded with 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]
The non-stretched film obtained using the condition recorded by table 2 is used as sample.It is adjusted in a manner that thickness is 20 μm
Winding speed manufactures film.It should be noted that the axis of orientation angle of film end be 5 degree hereinafter, percent thermal shrinkage measure after
Sample do not observe deformation.
[comparative example 4]
Using TOYOBO Co., ester (TOYOBO ESTER) (registered trademark) film E5100 (thickness is spun by Japan of LTD. manufactures
12 μm of degree).
[reference example 1]
As representative PBT films, the PBT films manufactured using commercially available Kansai Chemicals Co., Ltd.s.
The axis of orientation angle of film end is 5 degree hereinafter, the sample after percent thermal shrinkage measures does not observe deformation.
[table 2]
Industrial availability
For the polyester film of the present invention, caused fracture when being stretched for the PBT for inhibiting crystallization rate big is particularly logical
It is tied caused by the difference of cooling velocity when crossing the shear velocity of molten resin for inhibiting to discharge from mold in width direction, casting
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 be improved in harmony, impact resistance of the mechanical characteristic in MD and TD directions etc..
Claims (8)
1. the biaxial stretch-formed polybutylene terephthalate (PBT) film of a kind of 8 layers or more multiple stratifications, by comprising 60 mass % with
The polyester resin of upper polybutylene terephthalate (PBT) is formed, and the elongation at break of MD is the elongation at break of more than 155%, TD
For more than 105%, planar orientation be 0.12~0.14, impact strength is 0.05J/ μm or more and puncture intensity be 0.5N/ μm with
On.
2. the biaxial stretch-formed polybutylene terephthalate (PBT) film of 8 layers according to claim 1 or more multiple stratifications,
In, the difference of the maxima and minima of surface orientation coefficient that the overall width of the film after stretching is divided into 10 equal portions and is measured is
Less than 0.02.
3. the biaxial stretch-formed polybutylene terephthalate (PBT) film of 8 layers according to claim 1 or 2 or more multiple stratifications,
Wherein, the difference of the maxima and minima of the thickness in the overall width of the film after stretching is 0~25% relative to average thickness.
4. the biaxial stretch-formed polybutylene terephthalate (PBT) film of 8 layers according to claim 1 or 2 or more multiple stratifications,
Wherein, the upper limit of the MD percent thermal shrinkages of the film after stretching is 4%, the upper limit of TD percent thermal shrinkages is 3%.
5. the biaxial stretch-formed polybutylene terephthalate (PBT) film of 8 layers according to claim 1 or 2 or more multiple stratifications,
Wherein, the lower limit of the MD elasticity modulus of the film after stretching and TD elasticity modulus is 1GPa.
6. a kind of manufacturer of biaxial stretch-formed polybutylene terephthalate (PBT) film according to any one of claims 1 to 5
Method, which is characterized in that biaxial stretch-formed to the progress of following non-stretched film, the non-stretched film is to comprising more than 60 mass %
Obtained from the multiple stratification of 8 layers or more of the polyester resin progress of polybutylene terephthalate (PBT) is cast again.
7. the manufacturing method of biaxial stretch-formed polybutylene terephthalate (PBT) film according to claim 6, wherein, it is described
Multiple stratification uses and imported into extruder to the multilayer device of the melt line between mold.
8. the manufacturing method of the biaxial stretch-formed polybutylene terephthalate (PBT) film described according to claim 6 or 7, wherein,
The non-stretched film is stretched as successively biaxial drawing.
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 |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012110536 | 2012-05-14 | ||
| JP2012-110536 | 2012-05-14 | ||
| PCT/JP2013/062812 WO2013172214A1 (en) | 2012-05-14 | 2013-05-07 | Polyester film and method for producing same |
Related Child Applications (1)
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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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| CN104321372A CN104321372A (en) | 2015-01-28 |
| CN104321372B true 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 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
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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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|---|---|---|---|---|
| CN104321372B (en) * | 2012-05-14 | 2018-07-06 | 东洋纺株式会社 | Polyester film and its manufacturing method |
| 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 |
| JP6784256B2 (en) | 2015-04-24 | 2020-11-11 | 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 |
| JP6874277B2 (en) * | 2015-04-24 | 2021-05-19 | 東洋紡株式会社 | Biaxially stretched polyester film and its manufacturing method |
| US11299595B2 (en) * | 2015-08-19 | 2022-04-12 | Toyobo Co., Ltd. | Heat-shrinkable polyester film and package |
| 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 |
| KR20190125491A (en) * | 2017-03-28 | 2019-11-06 | 도요보 가부시키가이샤 | Biaxially-oriented polyester film and its manufacturing method |
| 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 |
| EP3636694A4 (en) * | 2017-06-06 | 2020-06-17 | Toyobo Co., Ltd. | 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 |
| JP6819816B2 (en) * | 2018-03-30 | 2021-01-27 | 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 |
| 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 |
| 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 |
| KR102612318B1 (en) * | 2019-02-26 | 2023-12-12 | 도요보 가부시키가이샤 | Biaxially oriented polyester film and method for producing the biaxially oriented polyester film |
| KR20210151922A (en) * | 2019-04-11 | 2021-12-14 | 바스프 에스이 | Polybutylene terephthalate thermoforming method |
| 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 |
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- 2013-05-07 KR KR1020147031598A patent/KR101961002B1/en active IP Right Grant
- 2013-05-07 MY MYPI2014703346A patent/MY172893A/en unknown
- 2013-05-07 WO PCT/JP2013/062812 patent/WO2013172214A1/en active Application Filing
- 2013-05-10 JP JP2013100065A patent/JP6194629B2/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6194629B2 (en) | 2017-09-13 |
| CN104321372A (en) | 2015-01-28 |
| JP6202146B2 (en) | 2017-09-27 |
| KR20150008872A (en) | 2015-01-23 |
| CN109111585A (en) | 2019-01-01 |
| JP2013256110A (en) | 2013-12-26 |
| JP2016172454A (en) | 2016-09-29 |
| MY172893A (en) | 2019-12-13 |
| WO2013172214A1 (en) | 2013-11-21 |
| TWI622608B (en) | 2018-05-01 |
| TW201406831A (en) | 2014-02-16 |
| KR101961002B1 (en) | 2019-03-21 |
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