CN107001666A - Polyester film - Google Patents
Polyester film Download PDFInfo
- Publication number
- CN107001666A CN107001666A CN201580064505.7A CN201580064505A CN107001666A CN 107001666 A CN107001666 A CN 107001666A CN 201580064505 A CN201580064505 A CN 201580064505A CN 107001666 A CN107001666 A CN 107001666A
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- Prior art keywords
- film
- polyester
- layers
- polyester film
- layer
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- Granted
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 78
- 229920001225 polyester resin Polymers 0.000 claims abstract description 29
- 239000004645 polyester resin Substances 0.000 claims abstract description 29
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 24
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 24
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 229920000728 polyester Polymers 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 121
- 238000000034 method Methods 0.000 description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 23
- 238000009998 heat setting Methods 0.000 description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000000137 annealing Methods 0.000 description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 14
- 239000012528 membrane Substances 0.000 description 13
- 230000009477 glass transition Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000000113 differential scanning calorimetry Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000004080 punching Methods 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000007405 data analysis Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical class C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010583 slow cooling Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- JSLMNNPQKHONFW-UHFFFAOYSA-N benzene naphthalene-1-carboxylic acid Chemical compound C1(=CC=CC2=CC=CC=C12)C(=O)O.C1=CC=CC=C1 JSLMNNPQKHONFW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229960003531 phenolsulfonphthalein Drugs 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
Polyester film, it is the polyester film that polyethylene terephthalate ratio shared in the polyester resin for constituting film is more than 60 weight %, and the percent thermal shrinkage in film length direction and width when carrying out being heat-treated for 30 minutes at 200 DEG C is less than 0.5%.The film of the low heat shrinkage and excellent in workability realized under heat resistance, particularly high temperature is provided.
Description
Technical field
The present invention relates to even if percent thermal shrinkage at high temperature also low polyester film.
Background technology
Polyester resin, particularly polyethylene terephthalate (being abbreviated as PET sometimes below), poly- 2,6- naphthalenedicarboxylic acids
Mechanical property, thermal characteristics, chemical reagent resistance, electrical characteristic, the mouldability of glycol ester (being abbreviated as PEN sometimes below) etc. are excellent
It is different, it is used for various uses.Polyester film, especially double axial orientated polyester film obtained from the polyester is made into film are excellent because of its
Mechanical property, electrical characteristic etc. and be used as solar cell backboard, water heater motor insulating materials, hybrid vehicle
The motor used for automobile air conditioning that is used in, motor with etc. electrically insulating material, magnetic pipe recording material, capacitor material,
The various industrial materials and Flexible Displays of packaging material, construction material, photo purposes, graphics use, thermographic transfer purposes etc.
The optical material of device, organic EL etc. transparent electrode substrate etc.
Among these purposes, for optical material (for example, film substrate (ITO (the Indium Tin of nesa coating
Oxide, indium tin oxide) evaporation substrate etc.)) purposes when, need to enter at a certain temperature to improve the electric conductivity of ito film
The step of row solidification, it is desirable to the percent thermal shrinkage of heat resistance, particularly reduction substrate.It is thus known that using low-heat in the purposes
The excellent film of shrinkage (patent document 1,2,3).
Prior art
Patent document
Patent document 1：Japanese Unexamined Patent Publication 3-13315 publications
Patent document 2：Japanese Unexamined Patent Publication 11-165350 publications
Patent document 3：Japanese Unexamined Patent Publication 2005-216706 publications.
The content of the invention
Problems to be solved by the invention
However, in order that the electric conductivity of ito film is higher than in the past and makes high performance optical device, it is necessary to improve curing schedule
Temperature.Therefore, for the polyester film used in the film substrate purposes of nesa coating, it is desirable to enter compared with existing product
Film percent thermal shrinkage under one step reduction high temperature.Among polyester film, in order that the heat receipts of the PET film of mechanical property, excellent heat resistance
Shrinkage is reduced, and film is effectively carried out into thermal finalization processing at high temperature.If however, in order to which the heat reduced under higher temperature is received
Shrinkage and implement thermal finalization processing at high temperature, then exist film flatness it is impaired the problem of.On the other hand, among polyester film,
The mechanical property of pen film is same with PET film excellent, in addition, the excellent heat resistance compared with PET film.But understand that pen film is had
Problem be：The PEN for constituting film possesses upright and outspoken molecular structure, therefore poor in processability, and film occurs damaged in processing.
The present invention problem in view of the background of the prior art there is provided the low polyester of percent thermal shrinkage under the high temperature conditions
Film.Further it is provided that flatness is good and polyester film of excellent in workability.
The solution used to solve the problem
In order to solve above-mentioned problem, the present invention takes following technical proposals.That is,
[I] polyester film, it is that polyethylene terephthalate ratio shared in the polyester resin for constituting film is 60 weights
More than % polyester film is measured, the percent thermal shrinkage in film length direction, width when carrying out being heat-treated for 30 minutes at 200 DEG C is equal
For less than 0.5%.
The polyester film of [II] according to [I], wherein, film length direction during heat treatment in 30 minutes is carried out at 200 DEG C
Percent thermal shrinkage, among the percent thermal shrinkage of width, at least the percent thermal shrinkage of any one is more than 0.01%.
The polyester film of [III] according to [I] or [II], wherein, film during heat treatment in 30 minutes is carried out at 220 DEG C
The percent thermal shrinkage of length direction, the percent thermal shrinkage of width are less than 0.5%, and at least the percent thermal shrinkage of any one is
More than 0.01%.
The polyester film of [IV] according to any one of [I] ~ [III], wherein, surveyed by noncontact laser microsurgical mirror
When determining the bumps of film, the bumps difference of film is less than 300 μm.
[V] according to polyester film any one of [I] ~ [IV], wherein, surface orientation coefficient be more than 0.145 and
Less than 0.165.
The polyester film of [VI] according to any one of [I] ~ [V], wherein, constituting the polyester resin of film has fusing point
(Tmf (DEG C)), and with the minor endothermic peak temperature (Tmeta (DEG C)) of more than 1.
The polyester film of [VII] according to [VI], wherein, constituting the polyester resin of film has the minor endothermic of more than 2
Peak (Tmeta (DEG C)), under the minimum Tmeta of temperature (Tmeta1) (DEG C) and temperature highest Tmeta (Tmeta2) (DEG C) is met
State relation：
Tmf-35(℃)≤Tmeta1(℃)<Tmeta2(℃)≤Tmf(℃)。
The polyester film of [VIII] according to any one of [I] ~ [VII], wherein, foregoing polyester film is at least to include 3 layers
Laminated polyester film, the fusing point (Tmo (DEG C)) for constituting the polyester resin of layer (A layer) is more than 260 DEG C, and (A layers) of the layer is constituted
The outmost surface of film.
The polyester film of [IX] according to [VIII], wherein, foregoing laminated polyester film includes 3 layers, constitutes layer (A layers)
The fusing point (Tmo (DEG C)) of polyester resin and constitute layer (B layer) polyester resin fusing point (Tmi (DEG C)) difference be more than 5 DEG C and
Less than 10 DEG C, described (A layers) composition top layer of layer, described (B layers) composition internal layer of layer.
The polyester film of [X] according to [IX], wherein, the thickness sum of layer (A layers) on top layer is constituted with constituting internal layer
The ratio between thickness of layer (B layers) is more than 1/8 and less than 1/4.
The polyester film of [XI] according to any one of [I] ~ [X], it is used for the film substrate of nesa coating.
The effect of invention
According to the present invention it is possible to provide the film of the low heat shrinkage and excellent in workability realized under heat resistance, particularly high temperature.
Embodiment
Hereinafter, enumerating concrete example and pin, the present invention is described in detail.
The polyester film of the present invention is that polyethylene terephthalate ratio shared in the polyester resin for constituting film is
More than 60 weight % polyester film.
Polyester referred to herein has dicarboxylic acids constituent and glycol constituent.It should illustrate, in this specification, structure
The minimum unit by hydrolyzing and resulting in by polyester is represented into composition.The ratio of polyethylene terephthalate is preferably
More than 70 weight %, more preferably more than 80 weight %.
The polyester film of the present invention carries out the heat receipts of the film length direction after heat treatment in 30 minutes and width at 200 DEG C
Shrinkage needs to be less than 0.5%.It is further preferred that by the present invention film handle 30 minutes at 200 DEG C after length direction with
The percent thermal shrinkage of width is less than 0.3%.
In general, when polyester film is stretched film, strand is in tensioning state (state of orientation) because of stretching.Therefore,
In the case where applying heat, there is a situation where that the tensioning of strand unwinds, film shrinks, flatness is deteriorated.As suppression by described
The method that contraction, flatness are deteriorated caused by hot, it is known that in order that (following by the structure of polyester molecule chain formed by stretching
Referred to as membrane structure) it is stable and use after stretching step provided with (being heat-treated this step of heat treatment at the specified temperature
Temperature is referred to as heat setting temperature) method.By implementing heat treatment step after stretching step, flatness, machinery can be obtained
Characteristic good film to a certain extent.Even however, by the film of such heat treatment step, if at high temperature, special
It is not that heat is applied to film with more than 200 DEG C of temperature, then constitutes the molecular structure disorder of film, flatness and be deteriorated.In other words, in order to
Reduction percent thermal shrinkage simultaneously makes the flatness of film keep good, it is necessary to which the structure for the molecule for constituting film is made into firm structure, shape
Into even if the structure at high temperature, particularly also stablized at a temperature of more than 200 DEG C.
Degree and heterogeneity that the strand of tensioning state shrinks by heat are in because of stretching.Therefore, even in film surface
Interior, percent thermal shrinkage, which can also be produced, there is fold in difference, film, and flatness is damaged.For example, polyester film is used to be used as electrically conducting transparent
During the ITO evaporation substrates of the film substrate of film, in the step (curing schedule etc.) after evaporation ito film, heat is applied to film negative
Carry.Now, if the flatness of film is damaged because of the thermal contraction of polyester film, the electric conductivity reduction of ito film, it is not preferable.
In addition, in general, when solidification temperature is high, the crystallite dimension of ito film becomes big, and the electric conductivity of ito film is improved, if
The crystallite dimension is big, then the tracing ability when film bending by substrate is made etc. is deformed is poor, and ito film is easily cracked.Can
The solidification temperature of tracing ability and electric conductivity is more than 200 DEG C and less than 220 DEG C when taking into account the deformation of ito film.Therefore, by making work
It is the film length direction at 200 DEG C of the temperature, 220 DEG C and the percent thermal shrinkage of width is less than 0.5%, can be by ITO
The flatness that film is solidified without damaging film at a proper temperature, is improved as the performance of transparent conductive substrate, so
It is preferred that.More preferably less than 0.3%.
As described above, from the viewpoint of the flatness of polyester film, the percent thermal shrinkage of the film at 200 DEG C, 220 DEG C is preferably
It is small, when polyester film is used for into ITO evaporation substrates, if the percent thermal shrinkage of the film at 200 DEG C, 220 DEG C is in length direction, width
It is more than 0.01% in any one of direction, then polyester film can be shunk without expanding because of heat, therefore, it is possible to suppress ito film hair
Raw cracking, is improved as the performance of transparent conductive substrate, so it is preferred that.It is further preferred that the heat receipts of the film at 200 DEG C, 220 DEG C
Shrinkage is more than 0.03% in any one of length direction, width.
In order that the percent thermal shrinkage of the polyester film of the present invention reaches above range, following methods can be enumerated：Specific
Under the conditions of implement polyester film film method (method first)；The polyester resin for constituting film is made to the method (side of specific structure
Method second)；The method that (method first) (method second) is combined.
First, illustrated for (method first).The polyester film of the present invention can compatibly be obtained by (method first),
Wherein, it is 60 weights to manufacture polyethylene terephthalate ratio shared in the polyester resin for constituting film by aftermentioned method
More than % polyester film is measured, is further annealed by aftermentioned method.
First, illustrated for the film-forming method of film.
The polyester of polyethylene terephthalate comprising more than 60 weight % is subjected to heating melting in extruder,
Then sprayed from tube head and obtain non-stretched sheet material, then implemented biaxial stretch-formed and obtain double axial orientated polyester film, in above-mentioned side
In method, by meeting following conditions, the percent thermal shrinkage at 200 DEG C can be reduced.
(1) by the polyester of melting from tube head spray and when making non-stretched sheet material, surface temperature be cooled to 10 DEG C with
It is closely sealed by electrostatic and cool and solidify on upper and less than 40 DEG C of drum, so as to make non-stretched sheet material.
(2) length by the non-stretched sheet material obtained in (1) under the temperature T1n (DEG C) for meeting following (i) formula along film
Biaxial stretch-formed to more than 10.0 times of the width (TD) of direction (MD) and film and less than 16.0 times of area multiplying power.
(i)Tg(℃)≤T1n(℃)≤Tg+40(℃)
Tg：Constitute the glass transition temperature (DEG C) of the polyester resin of polyester film.
(3) biaxially-stretched film obtained in (2) is carried out 1 second at the temperature (Th0 (DEG C)) for meeting following (ii) formulas
Above and less than 30 seconds thermal finalization processing, equably after Slow cooling, untill being cooled to room temperature, thus obtain polyester film.
(ii)Tmf-35(℃)≤Th0(℃)≤Tmf(℃)
Tmf：Constitute the fusing point (DEG C) of the polyester resin of polyester film.
By meeting the condition of (1) so as to obtain non-stretched sheet material, it is hereby achieved that be essentially the polyester film of amorphous,
In (2) later step, easily film can be assigned and be orientated, can be readily available that percent thermal shrinkage is small and mechanical property
Good film.
By meeting the condition of (2) so as to obtain biaxially-stretched film, it is possible thereby to assign the orientation of appropriateness to film, it can make
Into the good film of mechanical property.
By meeting the condition of (3) so as to complete crystalline orientation, it is possible thereby to which the polyester molecule chain for foring orientation is made
Stability Analysis of Structures, the film that percent thermal shrinkage is low and flatness is good.
It should illustrate, in (2), as biaxial stretch-formed method, any one of following methods can be used：By film
It is double successively that the stretching of the width (direction vertical with the length direction of film, TD) of length direction (MD) and film is separately carried out
Axle drawing process；In addition, biaxial stretching method while the stretching of progress length direction and width simultaneously.In addition, stretching
When temperature (T1n) (DEG C) is less than Tg (DEG C), it is difficult to stretched.When T1n (DEG C) is more than Tg+40 (DEG C), film frequently occurs sometimes
Breakage, it is impossible to obtain film by stretching.It is further preferred that Tg+10 (DEG C)≤T1n (DEG C)≤Tg+30 (DEG C).
It is preferably the method that step (3) is directly carried out in the state of grasping film two ends from the viewpoint of flatness.This
Outside, from the viewpoint of reduction percent thermal shrinkage, make while preferably on film width relative to film shrinkage in width 1 ~ 10%
The method of its thermal finalization.
For (3), the thermal contraction occurred in film is as described above, in the close temperature of the temperature with forming membrane structure
It is lower to occur, therefore in order to suppress percent thermal shrinkage of the film at a high temperature of more than 200 DEG C, it is important that improve heat setting temperature (Th0
(℃)).On the other hand, when being heat-treated at a temperature of heat setting temperature (Th0 (DEG C)) is more than Tmf (DEG C), film melt and
It can not be film-made.If in addition, being heat-treated at a temperature of excessively close to Tmf (DEG C), flatness is deteriorated sometimes.Therefore,
It is further preferred that Tmf-25 (DEG C)≤Th0 (DEG C)≤Tmf-10 (DEG C).If implementing thermal finalization processing, the poly- of film is constituted
Ester resin has the minor endothermic peak (Tmeta (DEG C)) for reflecting the heat setting temperature.Therefore, the polyester film of the present invention is constituted
Polyester resin preferably has minor endothermic peak.Also, the minor endothermic peak be preferably more than Tmf-35 (DEG C) and Tmf (DEG C) with
Under, more preferably more than Tmf-25 (DEG C) and Tmf-10 (DEG C) be below.
In addition, in order to reduce the percent thermal shrinkage under higher temperature, it is preferred that in order that foring the poly- of orientation in film
The structure of ester molecule chain is more consolidated, and implements annealing by following methods (4).
(4) by the film obtained in (3) in the case where meeting the heat treatment temperature Th1 (DEG C) of following (iii) formulas with more than 70 seconds and
The time of less than 600 seconds is annealed.As the method for carrying out the annealing, it can enumerate and go out roller and film with being arranged at film roll
The method that baking oven between takers-in is heat-treated (offline annealing) to film.
(iii) Tmf-35 (DEG C)≤Th1 (DEG C)≤Th0 (heat setting temperature) (DEG C).
By will further be moved back in the film that thermal finalization has been carried out under conditions of meeting (3) under conditions of (4) are met
Fire, can be such that the structure of the polyester molecule chain for foring orientation in film more consolidates, can be greatly reduced more than 200 DEG C that
Percent thermal shrinkage at a high temperature of sample.
In the case where Th1 (DEG C) is more than Th0 (heat setting temperature) (DEG C), in step (4), passed through by step (3)
Molecular chain structure in the film of regularization is destroyed, as a result, film significantly shrinks sometimes, flatness is deteriorated.On the other hand, exist
In the case that Th1 (DEG C) is less than Tmf-35 (DEG C), the percent thermal shrinkage under high temperature can not be reduced sometimes.It is less than Th0 in Th1 (DEG C)
In the case of (heat setting temperature) (DEG C), when particularly Th1 (DEG C) is sufficiently smaller than Th0 (heat setting temperature) (DEG C), for small
Endothermic peak (Tmeta) can be observed：Reflect the peak of the membrane structure formed by thermal finalization processing in step (3) and anti-
Mirror the peak by membrane structure formed by the annealing in step (4).Now, formed by the heat setting step of (3)
Membrane structure be not destroyed in the annealing process step of (4), therefore, it is possible to make the polyester molecule chain for foring orientation in film
Structure more consolidate.Now, the percent thermal shrinkage at a high temperature of more than 200 DEG C like that, the flatness of film can be greatly reduced
Become good.Therefore, constituting the polyester resin of the polyester film of the present invention preferably has the Tmeta (DEG C) of more than 2.Also,
Tmeta (DEG C) is present in the case of more than 2, the low Tmeta of temperature (Tmeta1) (DEG C) and the high Tmeta of temperature (Tmeta2)
(DEG C) meets Tmf-35 (DEG C)≤Tmeta1 (DEG C)<During Tmeta2 (DEG C)≤Tmf (DEG C), the good film of flatness can be obtained,
So it is preferred that.Can be by repeatedly the thermal finalization process step of (3), the annealing process step of (4).Determine by the heat of multiple (3)
Film obtained from type process step, the annealing process step of (4) has the Tmeta (DEG C) of more than 3 sometimes.With more than 3
Tmeta (DEG C) when, the minimum Tmeta (DEG C) of temperature is denoted as Tmeta1 (DEG C), and temperature highest Tmeta (DEG C) is denoted as
Tmeta2 (DEG C), preferably meets Tmf-35 (DEG C)≤Tmeta1 (DEG C)<Tmeta2 (DEG C)≤Tmf (DEG C) relation.
Then, illustrated for (method second).The polyester film of the present invention can be by method (method second) come compatibly
Obtain, wherein, being made includes at least 3 layers of stacked film, and it is more than 260 DEG C to constitute the fusing point (Tmo) of the resin of layer (A layers),
The outmost surface of (A layers) the composition film of layer.By the way that the structure of film is made into said structure, can reduce film percent thermal shrinkage,
Make flatness good, so it is preferred that.As the main component of the polyester film of the present invention polyethylene terephthalate it is molten
About 255 DEG C of point.That is, the polyester for constituting A layers includes the high-melting-point composition in addition to polyethylene terephthalate.Pass through
, can be in the film only formed by the resin for constituting internal layer (B layers) with the top layer (A layers) by being formed with dystectic resin
Thermal finalization processing, annealing are carried out at a high temperature of can not implementing in situation.By existing by being formed with dystectic resin
Top layer (A layers), even if carrying out thermal finalization processing, annealing at high temperature, can also prevent (B layer) of internal layer from melting.Can
Implement at this high temperature thermal finalization processing, annealing as a result, it is possible to be greatly reduced high more than as 200 DEG C
Percent thermal shrinkage under temperature.
It is further preferred that the fusing point (Tmo) for constituting the resin of layer (A layers) is more than 262 DEG C, described (A layers) composition film of layer
Outmost surface.In addition, from the viewpoint of processability, mechanical property, the internal layer (B layers) that top layer is not constituted is preferably poly- to benzene
Naphthalate.The fusing point Tmf (DEG C) for constituting the polyester resin of the polyester film of the present invention reflects containing more than 60 weight %
Main component, i.e. the fusing point of polyethylene terephthalate.
As the resin used in A layers, can enumerate PEN (hereinafter sometimes referred to PEN), poly- pair
Cyclohexyl diformazan alcohol ester (hereinafter sometimes referred to PCHT), polyphenylene sulfide (hereinafter sometimes referred to PPS) or they
Mixture.In addition, the adaptation in order to improve A layers and B layers, in the range of the application effect is not damaged, implementation further preferably
Mode is that a small amount of resin for constituting B layers is added into the resin for constitute A layers.B layers of resin is constituted in A layers of resin is constituted
Addition relative to constitute A layer of resin total amount be preferably 0.01 weight % less than 15 weight %, be more preferably 0.1
More than weight % and 5 below weight %.
In addition, constituting the molten of polyester resin of the fusing point (Tmo (DEG C)) of the resin of top layer (A layers) with constituting internal layer (B layers)
The difference (Tmo-Tmi (DEG C)) of point (Tmi (DEG C)) is preferably more than 5 DEG C and less than 15 DEG C.If the temperature difference is more than 15 DEG C,
During melting extrusion, stackability is deteriorated sometimes.On the other hand, if the temperature difference is less than 5 DEG C, it is difficult to assign by force A layers sometimes
Orientation.More preferably more than 5 DEG C and less than 10 DEG C.
Constitute thickness sum and the composition internal layer of the layer (A layer) on top layer the ratio between thickness of layer (B layers) (A layers of thickness it
With/B layers of thickness) it is preferably 1/16 ~ 1/2.During less than 1/16, the thickness of thin of top layer (A layers), protects B layers of function not sometimes
Fully, flatness, poor heat resistance.During more than 1/2, draftability is deteriorated sometimes.Constitute the thickness sum and structure of the layer (A layers) on top layer
The ratio between thickness of layer (B layers) into internal layer (A layers of thickness sum/B layers of thickness) is more preferably 1/8 ~ 1/4.By being set to this
Scope, can be made the excellent film of flatness, heat resistance, draftability.In addition, A layers of unilateral thickness is preferably more than 5 μm and 30
Below μm.In the case of above-mentioned stacking ratio is met, when A layers of unilateral thickness is less than 5 μm, flatness is poor sometimes, A layers
When unilateral thickness is more than 30 μm, draftability, processability are deteriorated sometimes.
When the polyester film of the present invention is made at least including 3 layers of stacked film, it is adapted to use following methods：For constituting layer
Each layer of folded film uses extruder, makes the raw materials melt of each layer, and they are used to the conjunction being arranged between extrusion device and tube head
Stream device is laminated in the molten state, is then introduced into tube head, is extruded from tube head to curtain coating drum, so as to process in flakes
Shape.The sheet material is cooled to closely sealed by electrostatic on more than 10 DEG C and less than 40 DEG C of drum and cooled and solidified in surface temperature,
So as to make non-stretched sheet material.The non-stretched sheet material is filmed by the above method (2) ~ (4), so as to obtain polyester film.
In the stacked film of this structure, the fusing point (Tmo (DEG C)) of resin on top layer is constituted higher than the resin for constituting film inner layer
Fusing point (Tmi (DEG C)), therefore when applying heat to film in heat setting step and annealing steps, inner layer resin is carried out by top layer
The effect of protection, compared with the PET film of individual layer, the structure of film is difficult to be destroyed.As a result, the flatness of film becomes better
It is good.
In addition, in the stacked film of this structure, embodiment further preferably is, the heat setting temperature as the formula that meets (iv)
The heat treatment of progress more than 1 second and less than 30 seconds under (Th0 (DEG C)), equably Slow cooling, is subsequently cooled to room temperature, by
This obtains polyester film, then with more than 70 seconds and less than 600 seconds under the annealing temperature Th1 (DEG C) for meeting following formula (v)
Time annealed.
(iv) Tmf-10 (DEG C)≤Th0 (heat setting temperature) (DEG C)≤Tmf (DEG C)
(v) Tmf-35 (DEG C)≤Th1 (DEG C)≤Th0 (heat setting temperature) (DEG C).
In the stacked film of this structure, the fusing point (Tmo (DEG C)) of resin on top layer is constituted higher than the polyester resin for constituting film
Fusing point Tmf (DEG C).That is, because surface layer as described above can protect the resin of internal layer, therefore, it is possible to improve heat setting temperature, energy
It is enough that thermal finalization is carried out at a temperature of close to Tmf (DEG C) without melting film.In the case of the formula that meets (iv), thermal finalization temperature
Degree reflects the Tmeta (DEG C) of heat setting temperature and fusing point overlap of peaks and can not observed close to Tmf (DEG C).On the other hand,
Due to membrane structure can be formed at higher temperatures after biaxial stretch-formed, therefore, it is possible to reach the annealing steps temperature of (4)
High temperature is without destroying membrane structure.As a result, even if stable membrane structure can also be made at high temperature, high temperature can be reduced
Under percent thermal shrinkage.
The percent thermal shrinkage of the film of the invention obtained in the above described manner at high temperature is low, in addition, flatness is also excellent.
The film of the present invention with noncontact laser microsurgical mirror by aftermentioned method when determining the bumps of film, and the bumps of film are poor
Preferably less than 300 μm.If concavo-convex difference is 0 μm, plane is essentially formed, therefore lower limit is more than 0 μm.
When the bumps difference on film surface is more than 300 μm, the electric conductivity after film processability is deteriorated sometimes, ITO is deposited is deteriorated, therefore not
It is preferred that.Concavo-convex difference is smaller, then the electric conductivity after ITO evaporations is got over and can improved.In order that the bumps difference on film surface is in above range,
It can enumerate：Film it is biaxial stretch-formed after provided with heat setting step so that after heat setting step be provided with heat setting temperature with
Under temperature under the method such as the step of annealed.More preferably less than 150 μm, particularly preferably less than 80 μm.
In addition, the surface orientation coefficient of the polyester film of the present invention is preferably more than 0.145 and less than 0.165.Surface orientation coefficient
It can be obtained by aftermentioned method by the refractive index of film.Surface orientation coefficient by the biaxially-stretched film formed such as PET, PEN is usual
Because the phenyl ring that is included in strand is arranged in parallel and become big along membrane plane.Phenyl ring be also in strand it is upright and outspoken, because
When this surface orientation coefficient is more than 0.165, phenyl ring is mostly arranged in parallel along membrane plane, so as to be cut etc by film progress bending
Processing when, film be sometimes prone to rupture.When surface orientation coefficient is less than 0.145, orientation is not realized because biaxial stretch-formed, therefore sometimes
Bad mechanical strength.
In addition, in the polyester film of the present invention, it is resistance to if the polyester resin for constituting film contains phosphoric acid and phosphoric acid alkali metal salt
Humid is excellent, so it is preferred that.As the method containing phosphoric acid and phosphoric acid alkali metal salt in polyester resin is made, it can enumerate poly-
Phosphoric acid and phosphoric acid alkali metal salt are added during the polymerization of ester resin.When the polyester film of the present invention is with A layers, B layers of stacked film, because
Humidity resistance is excellent and is preferably：Mode containing phosphoric acid and phosphoric acid alkali metal salt in only A layers；A layers, B layers contain phosphoric acid
With the mode of phosphoric acid alkali metal salt.When the humidity resistance of the polyester film of the present invention is good, it can be suitably used as more harsh
The ITO evaporation substrates used in the display that is used under environment, the display of such as auto-navigation system.
Processability, the flatness of the film obtained by the present invention are excellent, and percent thermal shrinkage at high temperature is small, therefore can fit
Ground is closed substrate purposes is deposited as ITO etc. transparency electrode and uses.
[evaluation method of characteristic]
A. the fusing point (Tmo, Tmi) (DEG C) of the resin of each layer is constituted
By the method based on JIS K 7121 (1999), the means of differential scanning calorimetry manufactured using セ イ コ ー electronics industries (strain)
Determining device, " ロ ボ ッ ト DSC-RDC220 ", data analysis uses デ ィ ス Network セ ッ シ ョ Application " SSC/5200 ", according to following main points
Sample is implemented to determine.
Into sample pot, each sample for weighing 5mg, 320 are heated to by sample with 20 DEG C/min of programming rate from 25 DEG C
℃(1stRUN).The means of differential scanning calorimetry for obtaining 1stRUN determines spectrogram (longitudinal axis is heat energy, and transverse axis is temperature).Obtain this
1stRun means of differential scanning calorimetry determines the peak position temperature of the crystallization melting peakss as endothermic peak in spectrogram, is denoted by fusing point
(℃).When observing the crystallization melting peakss of more than 2, the maximum peak position temperature of peak area is denoted as fusing point.
For sample, the resin for constituting each layer is only cut out from laminated polyester film using slicer, and for determining.
B. the fusing point (Tmf) (DEG C) of the polyester resin of polyester film is constituted
By the method based on JIS K 7121 (1999), the means of differential scanning calorimetry manufactured using セ イ コ ー electronics industries (strain)
Determining device, " ロ ボ ッ ト DSC-RDC220 ", data analysis uses デ ィ ス Network セ ッ シ ョ Application " SSC/5200 ", according to following main points
Sample is implemented to determine.
Into sample pot, each sample for weighing 5mg, 320 are heated to by sample with 20 DEG C/min of programming rate from 25 DEG C
℃(1stRUN).The means of differential scanning calorimetry for obtaining 1stRUN determines spectrogram (longitudinal axis is heat energy, and transverse axis is temperature).Obtain this
1stRun means of differential scanning calorimetry determines the peak position temperature of the crystallization melting peakss as endothermic peak in spectrogram, is denoted by fusing point
(℃).When observing the crystallization melting peakss of more than 2, the maximum peak position temperature of peak area is denoted as fusing point.
C. the minor endothermic peak (Tmeta1, Tmeta2) (DEG C) of the polyester resin of polyester film is constituted
For minor endothermic peak temperature Tmeta (DEG C), according to JIS K 7122 (1999), セ イ コ ー electronics industries (strain) are used
The means of differential scanning calorimetry of manufacture determines device, and " ロ ボ ッ ト DSC-RDC220 ", data analysis uses デ ィ ス Network セ ッ シ ョ Application " SSC/
5200 ", it is measured.5mg film is weighed into sample pot, 320 DEG C are heated to from 25 DEG C with 20 DEG C/min of programming rate
(1stRUN).The means of differential scanning calorimetry for obtaining 1stRUN determines spectrogram (longitudinal axis is heat energy, and transverse axis is temperature).Gained differential is swept
Retouch the minor endothermic peak temperature before the crystallization melting peakss in calorimetry spectrogram and be denoted as Tmeta (DEG C).Minor endothermic peak is difficult to see
During survey, by data analysis portion by the neighbouring amplification at peak, peak is read.It is when there is multiple minor endothermic peaks, temperature highest is micro-
Small endothermic peak is denoted as Tmeta1 (DEG C), and the minimum minor endothermic peak of temperature is denoted as into Tmeta2 (DEG C).
For the collection of illustrative plates read method at minor endothermic peak, using the blob detection function of analysis software, detected as peak
Among the temperature arrived, the endothermic peak detected at a temperature of less than fusing point is denoted as Tmeta.
D. the glass transition temperature (Tg) (DEG C) of the polyester resin of polyester film is constituted
According to JIS K 7121 (1999), the means of differential scanning calorimetry manufactured using セ イ コ ー electronics industries (strain) determines device
" ロ ボ ッ ト DSC-RDC220 ", data analysis uses デ ィ ス Network セ ッ シ ョ Application " SSC/5200 ", implements to survey according to following main points
It is fixed.
5mg sample is weighed into sample pot, sample is heated to 300 DEG C with 20 DEG C/min of programming rate from 25 DEG C
(1stRUN), keeps 5 minutes, then, quenching is to reaching less than 25 DEG C in this condition.Immediately followed by again with 20 DEG C/min
Programming rate be warming up to 300 DEG C to be measured from 25 DEG C, obtain 2ndRUN means of differential scanning calorimetry determine spectrogram (by the longitudinal axis
It is temperature by transverse axis for heat energy).The means of differential scanning calorimetry of the 2ndRUN is determined in spectrogram, in the step-like of glass transition
Change section office, the straight line and glass that equidistance is on y direction are started at as the straight line obtained from each baseline is extended
The point for changing the curve intersection of the step-like changing unit of transformation is obtained.Observe the step of the glass transition of more than 2
During the changing unit of shape, glass transition temperature is obtained respectively, and the average value of these temperature is denoted as to the glass transition of sample
Temperature (Tg) (DEG C).
D. the surface orientation coefficient (fn) of film
According to JIS K 7105 (1999), the Abbe formula refractometer manufactured using ア タ go (strain) obtains the refraction at 20 DEG C
Rate.Length direction refractive index (Nmd), width refractive index (Nd), the thickness direction refractive index (Nz) on film surface are determined, is calculated
Surface orientation coefficient (fn).
fn=(Nmd+Ntd)/2-Nz。
E. the percent thermal shrinkage (%) of film
According to JIS C 2318 (1997), the percent thermal shrinkage of film is determined.Film is cut into wide 10mm, long 150mm short strip shape.To survey
The mode that long part approximately reaches 100mm draws graticule on film, and the length of graticule is determined under conditions of 23 DEG C, L0 is denoted as.
Thereafter, it is being heated in the hot-air oven of set point of temperature (200 DEG C or 220 DEG C), is applying 2g counterweight and hang film, place 30 points
Clock.Film is taken out from baking oven and is cooled to after 23 DEG C, the length of graticule is determined, is denoted as L1.Film is obtained by following formula (vi)
Shrinkage factor.In measure, in the way of reaching 150mm length by film length direction or film width, cut out at 5 and surveyed at random
It is fixed.The respective average value of length direction, width is calculated, the percent thermal shrinkage of film is denoted as.
(vi) (film percent thermal shrinkage)=(L0-L1)/L0 × 100.
F. the flatness of film
As noncontact laser microsurgical mirror, the non-contact three-dimensional manufactured using three hawk light devices (strain) is determined device NH-SP3 and carried out
Evaluate.Analysis uses the NH softwares that (strain) Ling Guang companies manufacture.For film, film is cut into 120mm × 120mm.Make each side
Parallel to the length direction or width of film.4 sides of the film cut out are fixed on the measure platform of holding level with adhesive tape.
Under 3 d shape testing pattern, the surface configuration of film is determined.X-direction is set to film length direction, Y direction and is set to film width side
To.For determine spacing, X-direction be set to 100 μm, Y direction be set to 500 μm, measurement range is set to 100mm × 100mm's
Scope, Z axis multiplying power is set to 20 times.Calculate the peak of Z-direction and the difference (difference of height H (μm)) of minimum point.It is random from film
Ground will be in the shape cut out at 5, is calculated its average value, is evaluated in the following manner.
0≤H<80 are evaluated as A
80≤H<150 are evaluated as B
150≤H≤300 are evaluated as C
300<H is evaluated as D.
When being evaluated as A, flatness is most excellent.
G. the thickness (μm) of film
For film thickness, using micrometer, according to JIS K7130 (1992) A-2 methods, in the state of overlapping 10 films, pin
To determining thickness at arbitrary 5.Film thickness is used as by its average value divided by 10.
H. each thickness degree (μm) of stacked film
When film is stacked film, the thickness of each layer is obtained by following methods.Along the direction parallel with film width, with section
Machine-cut membrane section.With scanning electron microscope, the section is observed with 5000 times of multiplying power, the thickness ratio for being laminated each layer is obtained
Rate.According to the stacking ratio and above-mentioned film thickness obtained, the thickness of each layer is calculated.
I. punching property
The test film clicker press machine manufactured using macromolecule gauge (strain), stacked film is punched into No. 5 types described in JIS K-6251
Dumbbell shape.The piece number M that end face is damaged, peel off occurs when counting overlapping 50 films and being punched, punching property is evaluated.
0≤M≤9 ：Punching property is A
10≤M≤20 ：Punching property is B
21≤M≤30 ：Punching property is C
31≤M ：Punching property is D.
A is most excellent, and D is worst.
J. inherent viscosity IV
Polymer blend is dissolved in o-chlorphenol 100ml (solution concentration C=1.2g/dl), determined using Ostwald viscosimeters
Viscosity of the solution at 25 DEG C.In addition, similarly determining the viscosity of solvent.Using resulting solution viscosity, solvent viscosity, pass through
Following formula (c) calculates [η] (dl/g), and institute's value is denoted as into inherent viscosity (IV).
(c)ηsp/C=[η]+K[η]2・C
(here, η sp=(solution viscosity (dl/g)/solvent viscosity (dl/g)) -1, K are Huggins constants (being 0.343)).
K. terminal carboxyl group amount
According to Maulice method, terminal carboxyl group amount is determined by following methods.(document：M.J.Maulice,F.
Huizinga, Anal.Chim.Acta,22 363(1960))。
2g is determined into sample (polyester resin (raw material) or only isolate the P1 layers of layered product obtained from sample) at 80 DEG C
At a temperature of be dissolved in orthoresol/chloroform (weight ratio be 7/3) 50mL, titrated by 0.05N KOH/ methanol solutions, survey
Determine end carboxy concentration, represented with equivalent/polyester 1t (eq./t) value.Should illustrate, indicator during titration using phenol red,
The pink moment will be become from yellow green as titration end-point.It should illustrate, be dissolved with the solution for determining sample and there is nothing
During the insoluble matters such as machine particle, implement following corrections：Solution is filtered and the weight of insoluble matter is determined, subtracted from sample weight is determined
The weight of insoluble matter is gone, institute's value is regard as measure sample weight.
L. Film making properties
In film-forming process, film number of times damaged in 1 hour is counted, A is evaluated as during less than 1 time, 1 time less than 3 times
When be evaluated as B, 3 times less than 5 times when be evaluated as C, be more than 5 times when be evaluated as D.A Film making properties are most good, D system
Film is worst.
It should illustrate in said determination, when length direction, the width of the film determined are unknown, will have in film
The direction of largest refractive index is regarded as length direction, and the direction vertical with length direction is regarded as into width.In addition, for film
The direction of largest refractive index, can be determined the directive refractive index of institute of film to obtain by refractometer, can also pass through profit
Determine slow-axis direction to obtain with measuring difference of phases device (double refraction detection device) etc..
M. the humidity resistance of film
Stacked film is cut out to 1cm × 20cm size, base respectively in the way of length direction width of the long side parallel to film
In ASTM-D882 (1997), determine fracture when being stretched with 5cm fixture spacing, the draw speed of 300mm/ minutes and stretch
Long rate.It should illustrate, sample number is n=5, in addition, after the length direction, width for film are measured respectively, obtaining it
Average value, be denoted by the elongation at break E0 of film.
Then, the pressure cooker manufactured by タ バ イ エ ス ペ ッ Network (strain), temperature be 125 DEG C, relative humidity be 100%
After being handled under RH high wet heat condition the film equally cut out, elongation at break is determined.It should illustrate, be determined as n=5, pin
Length direction, width to film are measured respectively, are averaged value and are denoted as elongation at break E1.Broken using resulting
Elongation E0, E1 are split, percent retention of elongation is calculated by following formula (a).The ground exception processes time, will extend in units of one hour
Rate conservation rate reaches that less than 50% processing time is denoted as elongation half-life period.
(d) percent retention of elongation (%)=E1/E0 × 100.
The humidity resistance of film is judged according to resulting elongation half-life period as follows.
Elongation half-life period is the situation of more than 30 hours：A
Elongation half-life period is 20 hours less than the situation of 30 hours：B
Elongation half-life period is less than the situation of 20 hours：C.
Embodiment
Hereinafter, for the present invention, enumerate embodiment and illustrate, but the present invention is not necessarily defined in them.
[PET-A manufacture] is entered using antimony trioxide as catalyst by conventional method by terephthalic acid (TPA) and ethylene glycol
Row polymerization, obtains melt polymerization PET.Gained melt polymerization PET glass transition temperature is 81 DEG C, fusing point is 255 DEG C, characteristic
Viscosity is that 0.62, terminal carboxyl group amount is 20eq./t.Then, melt polymerization PET is made to carry out solid phase by conventional method, from
And obtain PET-A.Gained PET-A glass transition temperature is 82 DEG C, fusing point is 255 DEG C, inherent viscosity is 0.85, end carboxylic
Base unit weight is 11eq./t.
[PEN-A manufacture] implements ester friendship using manganese acetate as catalyst by 2,6- naphthalene dicarboxylic acids dimethyl ester and ethylene glycol
Change reaction.After ester exchange reaction terminates, using antimony trioxide as catalyst, PEN-A is obtained by conventional method.Gained PEN-
A glass transition temperature is 124 DEG C, fusing point is 265 DEG C, inherent viscosity is that 0.62, end carboxy concentration is 25eq./t.
Terephthalic acid (TPA) and ethylene glycol are used as raw material by [PET-B manufacture], using antimony trioxide as catalyst, are carried out
Polymerization.While antimony trioxide is added, phosphoric acid and sodium dihydrogen phosphate dihydrate are dissolved in molten obtained from ethylene glycol by addition
Liquid.Phosphoric acid by relative to PET equivalent to 2.0mol/t in the way of be added, sodium dihydrogen phosphate dihydrate is with relative to PET
Mode equivalent to 1.7mol/t is added.In addition, being inactivated to suppress polymerization catalyst because of phosphorus compound, in addition phosphorus
While compound, the manganese acetate relative to PET equivalent to 2.4mol/t is added, makes polymerisation carry out obtaining PET-C.
Gained PET-C glass transition temperature is 81 DEG C, fusing point is 255 DEG C, inherent viscosity be 0.68, terminal carboxyl group amount be 20eq./
t.Then, PET-C is carried out solid phase by conventional method, obtain PET-B.Gained PET-B glass transition temperature is
82 DEG C, fusing point be 255 DEG C, inherent viscosity be that 0.85, terminal carboxyl group amount is 11eq./t.
2,6- naphthalene dicarboxylic acids dimethyl ester and ethylene glycol are used as raw material by [PEN-B manufacture], and catalysis is used as using manganese acetate
Agent, implements ester exchange reaction.After ester exchange reaction terminates, with antimony trioxide as the catalyst to being polymerize.In addition three
While antimony oxide, solution obtained from phosphoric acid and sodium dihydrogen phosphate dihydrate are dissolved in ethylene glycol by addition.Phosphoric acid is with relative
Be added in modes of the PET equivalent to 2.0mol/t, sodium dihydrogen phosphate dihydrate with relative to PET equivalent to 1.7mol/t
Mode be added, polymerisation is carried out so as to obtaining PEN-B.Gained PEN-B glass transition temperature be 124 DEG C,
Fusing point is 265 DEG C, inherent viscosity is that 0.62, end carboxy concentration is 20eq./t.
(embodiment 1)
As the resin for constituting top layer, PEN-A is set to 100 mass parts, after being dried in vacuo 2 hours at 160 DEG C, put into crowded
Go out in machine 1.In addition, as the resin for constituting internal layer, after 100 mass parts PET-A are dried in vacuo 2 hours at 160 DEG C, input
Into extruder 2.Each raw material is melted at a temperature of described in table in extruder, by converging device with put into squeeze
The mode for going out two top layers of the resin formation film of machine 1 is collaborated, and extrudes to surface temperature on 25 DEG C of curtain coating drum, to make
Make the laminates for possessing 3-tier architecture.Then, after the piece is preheated with the roller group of heating, along length at a temperature of 95 DEG C
Spend after the stretching that direction (MD directions) carries out 3.2 times, cooled down with temperature for 25 DEG C of roller group, so as to obtain uniaxial tension
Film.The two ends of gained monadic stretching membrane are clamped with fixture, and the temperature in stenter is edge in 110 DEG C of heating zone
The width (TD direction) vertical with length direction and stretch 3.5 times.And then, continue in heat-treatment zone in stenter
The thermal finalization of implementation 10 seconds at a temperature of 240 DEG C.The step of by thermal finalization, make film wide relative to film along film width
Degree shrinks 5%.Then, in cooling zone equably after Slow cooling, batched, so as to obtain laminated polyester film.And then, use
It is arranged at the hot-air oven that film roll goes out between roller and film takers-in, the time at a temperature of 220 DEG C to be heat-treated to film
The mode of 5 minutes is reached, gained film is implemented to make annealing treatment, the film that thickness is 100 μm is obtained.Each characteristic of film is shown in table
In.It is at 200 DEG C percent thermal shrinkage is low and flatness also special good film.
(embodiment 2-4)
It is as shown in the table, and ground changes composition, the film forming condition of resin, in addition, is filmed in the way of similarly to Example 1.
The characteristic of film is shown in table.It is at 200 DEG C percent thermal shrinkage is low and flatness also special good film.
(embodiment 5)
It is as shown in the table, and ground changes the heat setting temperature of film, offline annealing temperature, in addition, in the way of similarly to Example 1
Obtain the film that thickness is 100 μm.Each characteristic of film is shown in table.Because heat setting temperature is near film fusing point, therefore only to see
Observe 1 Tmeta.Understand the film be percent thermal shrinkage at 200 DEG C it is low and 220 DEG C at percent thermal shrinkage is low, flatness is excellent
Film.
(embodiment 6-8)
It is as shown in the table, and ground changes composition, the film forming condition of resin, in addition, is film-made in the way of similarly to Example 5.By film
Characteristic be shown in table.It is at 220 DEG C percent thermal shrinkage is low and flatness also special good film.
(embodiment 9-14,22)
It is as shown in the table, and ground changes stacking ratio, the thickness of film of film, in addition, is film-made in the way of similarly to Example 1.By film
Characteristic be shown in table.In embodiment 9, the stacking ratio of top layer (A layers) is big, therefore Film making properties, processability are slightly poor, but is resistant to
It is practical.In embodiment 11, the stacking of top layer (A layers) is than small, thickness of thin, therefore the function of protection internal layer (B layers) is reduced, flatness
Difference.In embodiment 13, the unilateral thinner thickness of top layer (A layers), therefore the function of protection internal layer (B layers) is reduced, flatness is slightly poor,
But it is resistant to practicality.In embodiment 22, the unilateral thickness of top layer (A layers) is thicker, therefore Film making properties, processability are slightly poor, but energy
Enough tolerances are practical.
(embodiment 15-17)
It is as shown in the table, and ground changes the composition of resin, the offline annealing temperature of film, in addition, in the way of similarly to Example 5
Film.The characteristic of film is shown in table.Compared with Example 5, offline annealing temperature is low, therefore the percent thermal shrinkage at 220 DEG C is omited
Difference, but show the excellent characteristic of flatness.
(embodiment 18,21)
The resin for constituting film is set as only polyethylene terephthalate, it is as shown in the table, and ground sets film forming condition, manufacture is single
The film of film.The characteristic of film is shown in table.In embodiment 18, flatness is with implementing although the percent thermal shrinkage at 200 DEG C is excellent
It is slightly poor that example 1 is compared, but is resistant to practicality.In embodiment 21, heat setting temperature is identical with annealing temperature, therefore percent thermal shrinkage is excellent
It is different.Although flatness is slightly poor, practicality is resistant to.
(embodiment 19)
Ground setting that it is as shown in the table constitutes A layers of resin composition, in addition, film is obtained in the way of similarly to Example 1.By film
Characteristic be shown in table.A layers of fusing point is understood less than 260 DEG C, flatness is slightly poor.
(embodiment 20)
The resin used in A layers is set to PCHT, in addition, film is obtained in the way of similarly to Example 1.PCHT is used
The copolyester13319 of イ ー ス ト マ Application ケ ミ カ Le company manufacture.The characteristic of film is shown in table.It is percent thermal shrinkage,
The excellent film of flatness.
(embodiment 23-25)
The resin used in A layers is set to PEN-B, the resin used in B layers is set to PET-B, in addition, with embodiment
1 same mode obtains film.The characteristic of film is shown in table.It is the excellent film of percent thermal shrinkage, flatness, humidity resistance.
(comparative example 1,2)
The resin for constituting film is set as only polyethylene terephthalate, it is as shown in the table, and ground sets film forming condition, manufacture is single
The film of film.The characteristic of film is shown in table.In comparative example 1, Tmeta1 temperature is low and less than Tmf-35 DEG C, therefore percent thermal shrinkage
Difference.In comparative example 2, heat setting temperature is high and identical with Tmf, therefore Film making properties are poor, can not obtain film.
(comparative example 3,4)
The resin for constituting film is set as only PEN, is filmed under the stretching condition described in table.The characteristic of gained film is shown
In table.In comparative example 3, only carry out in thermal finalization, comparative example 4, implement offline annealing after heat setting step.Due to it not
Using PET as the film of main component, greatly, therefore processability is substantially deteriorated surface orientation coefficient (fn).
(comparative example 5,6)
Ground change that it is as shown in the table constitutes A layers of resin composition, film forming condition, in addition, the system in the way of similarly to Example 1
Film.Membrane property is shown in table.
In comparative example 5, Tmeta1 temperature is low and less than Tmf-35 DEG C, therefore percent thermal shrinkage is substantially deteriorated.Comparative example 6
In, without offline annealing steps, therefore percent thermal shrinkage is substantially deteriorated.
[table 1]
。
[table 2]
。
[table 3]
。
[table 4]
。
[table 5]
。
[table 6]
。
[table 7]
。
[table 8]
。
[table 9]
。
[table 10]
。
Industrial applicibility
Polyester film not only flatness, the excellent in workability of the present invention, heat resistance is also excellent.Therefore, even if polyester film of the invention
In the step of the hot environment of transparency electrode evaporation etc., its film change in shape is also few, can be compatibly as optical device base
Plate purposes is used.
Claims (11)
1. polyester film, it is that polyethylene terephthalate ratio shared in the polyester resin for constituting film is 60 weight %
Polyester film above, film length direction, the percent thermal shrinkage of width when heat treatment in 30 minutes is carried out at 200 DEG C are
Less than 0.5%.
2. polyester film according to claim 1, wherein, film length direction when carrying out heat treatment in 30 minutes at 200 DEG C,
Among the percent thermal shrinkage of width, at least the percent thermal shrinkage of any one is more than 0.01%.
3. polyester film according to claim 1 or 2, wherein, film length side during heat treatment in 30 minutes is carried out at 220 DEG C
To percent thermal shrinkage, width percent thermal shrinkage be less than 0.5%, and at least the percent thermal shrinkage of any one be 0.01% with
On.
4. the polyester film according to any one of claim 1 ~ 3, wherein, film is determined by noncontact laser microsurgical mirror
When concavo-convex, the bumps difference of film is less than 300 μm.
5. the polyester film according to any one of claim 1 ~ 4, wherein, surface orientation coefficient be more than 0.145 and 0.165 with
Under.
6. the polyester film according to any one of claim 1 ~ 5, wherein, constituting the polyester resin of film has fusing point (Tmf
(DEG C)), and with the minor endothermic peak temperature (Tmeta (DEG C)) of more than 1.
7. polyester film according to claim 6, wherein, constituting the polyester resin of film has the minor endothermic peak of more than 2
(Tmeta (DEG C)), the minimum Tmeta of temperature (Tmeta1) (DEG C) meets following with temperature highest Tmeta (Tmeta2) (DEG C)
Relation：
Tmf-35(℃)≤Tmeta1(℃)<Tmeta2(℃)≤Tmf(℃)。
8. the polyester film according to any one of claim 1 ~ 7, wherein, the polyester film is at least to include 3 layers of stacking
Polyester film, the fusing point (Tmo (DEG C)) for constituting the polyester resin of layer (A layers) is more than 260 DEG C, the table of (A layers) the composition film of layer
Face.
9. polyester film according to claim 8, wherein, the laminated polyester film includes 3 layers, constitutes the polyester of layer (A layers)
The difference of the fusing point (Tmi (DEG C)) of the fusing point (Tmo (DEG C)) of resin and the polyester resin of composition layer (B layers) is more than 5 DEG C and 10 DEG C
Hereinafter, described (A layers) composition top layer of layer, described (B layers) composition internal layer of layer.
10. polyester film according to claim 9, wherein, the thickness sum of layer (A layers) on top layer is constituted with constituting internal layer
The ratio between thickness of layer (B layers) is more than 1/8 and less than 1/4.
11. the polyester film according to any one of claim 1 ~ 9, it is used for the film substrate of nesa coating.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014241226 | 2014-11-28 | ||
| JP2014-241226 | 2014-11-28 | ||
| PCT/JP2015/081140 WO2016084568A1 (en) | 2014-11-28 | 2015-11-05 | Polyester film |
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| Publication Number | Publication Date |
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| CN107001666A true CN107001666A (en) | 2017-08-01 |
| CN107001666B CN107001666B (en) | 2020-09-01 |
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| CN201580064505.7A Active CN107001666B (en) | 2014-11-28 | 2015-11-05 | Polyester film |
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| Country | Link |
|---|---|
| JP (1) | JP6565683B2 (en) |
| KR (1) | KR102402833B1 (en) |
| CN (1) | CN107001666B (en) |
| TW (1) | TWI685510B (en) |
| WO (1) | WO2016084568A1 (en) |
Cited By (3)
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|---|---|---|---|---|
| CN110733223A (en) * | 2018-07-19 | 2020-01-31 | 日东电工株式会社 | Polyester film, protective film laminate, and method for producing protective film |
| CN111108146A (en) * | 2017-09-22 | 2020-05-05 | 三菱化学株式会社 | Copolyester film |
| WO2024050690A1 (en) * | 2022-09-06 | 2024-03-14 | 扬州纳力新材料科技有限公司 | Composite polyester film, preparation method therefor, and use thereof |
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| JP7234563B2 (en) * | 2018-10-05 | 2023-03-08 | 東レ株式会社 | polyethylene terephthalate film |
| AU2019369562B2 (en) * | 2018-10-31 | 2022-10-27 | Jfe Steel Corporation | Film for Coating Metal Sheet and Resin Coated Metal Sheet |
| KR102378969B1 (en) * | 2018-11-09 | 2022-03-25 | 주식회사 엘지화학 | Method for Manufacturing Conductive Polymer Substrate |
| CN113811750B (en) * | 2019-06-28 | 2024-03-08 | 富士胶片株式会社 | Sheet set for pressure measurement and sheet for pressure measurement |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI685510B (en) | 2020-02-21 |
| TW201625714A (en) | 2016-07-16 |
| JP6565683B2 (en) | 2019-08-28 |
| CN107001666B (en) | 2020-09-01 |
| JPWO2016084568A1 (en) | 2017-09-07 |
| KR20170090410A (en) | 2017-08-07 |
| KR102402833B1 (en) | 2022-05-27 |
| WO2016084568A1 (en) | 2016-06-02 |
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