CN101618600A - Longitudinal uniaxial drawing polyethylene naphthalate polymer film and manufacturing method thereof - Google Patents
Longitudinal uniaxial drawing polyethylene naphthalate polymer film and manufacturing method thereof Download PDFInfo
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- CN101618600A CN101618600A CN200910149535A CN200910149535A CN101618600A CN 101618600 A CN101618600 A CN 101618600A CN 200910149535 A CN200910149535 A CN 200910149535A CN 200910149535 A CN200910149535 A CN 200910149535A CN 101618600 A CN101618600 A CN 101618600A
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- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 title claims abstract description 29
- 239000011112 polyethylene naphthalate Substances 0.000 title claims abstract description 29
- -1 polyethylene naphthalate Polymers 0.000 title claims abstract description 23
- 229920006254 polymer film Polymers 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- UHPJWJRERDJHOJ-UHFFFAOYSA-N ethene;naphthalene-1-carboxylic acid Chemical compound C=C.C1=CC=C2C(C(=O)O)=CC=CC2=C1 UHPJWJRERDJHOJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002834 transmittance Methods 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002952 polymeric resin Substances 0.000 abstract 1
- 229920003002 synthetic resin Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 130
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- 239000012528 membrane Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
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- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 5
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- 230000009477 glass transition Effects 0.000 description 4
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 238000007605 air drying Methods 0.000 description 2
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- PWFCXQJXVJZYMH-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1(=CC=CC=C1)C1CCC2=CC=CC=C12 Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1(=CC=CC=C1)C1CCC2=CC=CC=C12 PWFCXQJXVJZYMH-UHFFFAOYSA-N 0.000 description 1
- HJAVFEACTVVVLS-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1(=CC=CC=C1)OC1=CC=CC=C1 Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1(=CC=CC=C1)OC1=CC=CC=C1 HJAVFEACTVVVLS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
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- 229940051250 hexylene glycol Drugs 0.000 description 1
- 210000004276 hyalin Anatomy 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a kind of longitudinal uniaxial drawing polyethylene naphthalate polymer film having excellent heat resistance and uneven thickness, high birefringence, very little distribution and excellent transparency, and being useful in the optical application field, and a method for manufacturing the same. The longitudinal uniaxial drawing polyethylene naphthalate polymer film is characterized in that it is obtained by uniaxially drawing non-drawing polyethylene naphthalate polymer film formed by polyethylene naphthalate polymer resin having a inherent viscosity of 0.4 to 0.8dk/g, its total beam transmissivity is above 90%, a difference Deltan of a refraction index nx in the drawing direction and a refraction index ny in a width direction vertical to the drawing direction is 0.25 to 0.35, an angle of a slow shaft is less than +/-1 DEG, its thickness after drawing is 20 to 100[Mu]m, its film width is 200 to 1000 mm.
Description
Technical field
High birefringence, high hyaline membrane and manufacture method thereof that the vertical monadic stretching membrane by PEN that the present invention relates to use in the Optronics field is made.Also relate to the LCD that is suitable for the requirement high birefringence improves the PEN of film with optical compensation films, the brightness of LCD backlight lamp vertical monadic stretching membrane.
Background technology
So far; use the film of high birefringence (Δ n) as the adhesive of the polarizing coating that uses in the optical compensation material of field of liquid crystal, the liquid crystal display easy inspectionization with mold release film, and as the diaphragm of the dichroism polarizer that uses in the optical light filter equiwavelength plate of optic pick-up device, digital camera, polarized lens, the polarization sunglasses.
So far, in this field, the film of high birefringence (Δ n) uses the monadic stretching membrane of Merlon more.(Δ n * d) is (d is the thickness (μ m) of film) about about 1500nm to the maximal phase potential difference Re of Merlon monadic stretching membrane.
But, with in the past Merlon uniaxial tension and be used for these purposes fields and have restriction technically.That is, in order to make the more film of high birefringence efficiently, residual have a following problem to be solved: the film in the stretching ruptures easily, be easy to generate birefringent inhomogeneous, the film of drawn in uneven thickness big and bad etc.
So far, method, device as vertical uniaxial tension have proposed patent documentation 1～5 etc.In the patent documentation 1, following method has been proposed: during the longitudinal stretching polymer film, make the heating measurer variant at the both ends of film and central portion, promptly be adjusted to the film both ends to add heat bigger than film central portion, obtain the longitudinal stretching film.In addition, in patent documentation 2, also proposed the manufacture method of vertical uniaxial tension phase retardation film, the draft temperature gradient is set and has implemented at the width of thermoplastic film in the method.In addition, in the patent documentation 3, not stretched width direction but the long side direction (direction of travel of film) that stretching, set for the temperature of the moving direction front face side of sheet material and compare, the temperature of the moving direction side of sheet material is a high temperature, the heat of giving sheet material when therefore stretching increases successively, can suppress the crystallization of film at the stretching initial stage.
In addition, proposed freely to change the longitudinal tensile fixture in the gap between draw roll in the patent documentation 4, proposed in the patent documentation 5, near the method that makes the film stabilisation and stretch with nip rolls (pinch roll) away from the point of low speed roller at film in low speed roller side.
But,, exist to be difficult to successfully carry out the problem that high magnification stretches for existing stretching technique, stretching device.Even use nip rolls,, therefore be difficult to make the starting point stabilisation of stretching owing to its high tensile stress in low speed roller side.In addition, make film have the drawing process of temperature, heat gradient at the film width in the longitudinal stretching, it is numerous and diverse that device becomes, but also have the problem of its control difficulty.
Patent documentation 1: Japanese kokai publication hei 10-244586 communique
Patent documentation 2: Japanese kokai publication hei 08-101306 communique
Patent documentation 3: Japanese kokai publication hei 04-282225 communique
Patent documentation 4: Japanese kokai publication hei 08-118466 communique
Patent documentation 5: Japanese kokai publication hei 08-011204 communique
Summary of the invention
The objective of the invention is to address the above problem, excellent heat resistance is provided, excellence in uneven thickness, high birefringence, it distributes very little and have the excellent transparency, useful longitudinal uniaxial drawing polyethylene naphthalate polymer film in the optical applications field.
According to the present invention, the following realization of above-mentioned purpose of the present invention and advantage:
(1) longitudinal uniaxial drawing polyethylene naphthalate polymer film, it is characterized in that: the not stretching poly (ethylene naphthalate) film that is formed at the PEN resin of 0.4～0.8dl/g scope by inherent viscosity is carried out vertical uniaxial tension and obtains, total light transmittance is more than 90%, the refractive index n x of draw direction and with the difference Δ n of the refractive index n y of the width of its quadrature be 0.25～0.35, the angle of slow axis is below ± 1 °, thickness after the stretching is 20～100 μ m, and film is wide to be the scope of 200～1000mm.
(2) above-mentioned (1) described longitudinal uniaxial drawing polyethylene naphthalate polymer film, wherein, poly-2 of poly (ethylene naphthalate) film does not stretch, the copolymerization ratio of 6-(ethylene naphthalate) is 80 moles more than the %, birefringence n is below 0.003, Tg is 120～130 ℃, and refractive index is 1.644～1.646, and density is 1.328～1.332g/cm
3, thickness is 30～300 μ m, width is 300～2000mm.
(3) manufacture method of above-mentioned (1) described longitudinal uniaxial drawing polyethylene naphthalate polymer film, it is characterized in that: use the roll-type longitudinal stretching machine that has nip rolls (nip roll), preceding half (in advance) heating clamber, later half (longitudinal stretching) heating clamber, nip rolls from the inlet beginning successively, the temperature of preceding half (in advance) heating clamber is set at 90～110 ℃, the temperature of later half (longitudinal stretching) heating clamber is set at 115～135 ℃, the draw speed of later half (longitudinal stretching) heating clamber is set at 5～15 times/minute, gives 3.5～5.5 times stretching ratio.
Description of drawings
Fig. 1 is the skeleton diagram of the stretching device that uses among the present invention of expression.
Fig. 2 is the key diagram of the definition of draw speed among the present invention.
Symbol description
1. nip rolls
2. preceding half (in advance) heating clamber
3. later half (longitudinal stretching) heating clamber
4. nip rolls
L: stretching distance (m)
L=L/100: hundred parts of distances (m) after cutting apart
V (1): the film initial velocity (m/min) when 100 parts of stretching distances are cut apart
V (100): the film terminal velocity (m/min) when 100 parts of stretching distances are cut apart
T: stretching time
The stretching time of the n part after hundred parts of t (n): l=L/V (n) are cut apart
B: stretching ratio
Ev: draw speed (doubly/minute)
Ev＝B/T
The specific embodiment
Below the present invention is described in detail.
(PEN)
The main repetitive of aromatic polyester that constitutes uniaxial orientation polyester film of the present invention is by 2, and the 6-(ethylene naphthalate) constitutes.2,6-(ethylene naphthalate) unit is preferably 80 moles of whole repetitives more than the %, more preferably 90 moles of %.With 2, the repetitive that 6-(ethylene naphthalate) unit is different can be by using 2, and other dicarboxylic acids and/or other dicarboxylic acids beyond the ethylene glycol and/or other glycol etc. beyond 6-naphthalenedicarboxylic acid and/or the ethylene glycol import as copolymer composition.
As this copolymer composition, can use to have the compound that 2 esters form functional group.As this copolymer composition, can enumerate for example oxalic acid, adipic acid, phthalic acid, decanedioic acid, dodecanedicarboxylic acid, butanedioic acid, M-phthalic acid, 5-sodium is for sulfoisophthalic acid, terephthalic acid (TPA), 2-potassio sulfoisophthalic acid, 2, the 7-naphthalenedicarboxylic acid, 1, the 4-cyclohexane cyclohexanedimethanodibasic, 4,4 '-biphenyl dicarboxylic acid, the phenyl indan dioctyl phthalate, diphenyl ether dioctyl phthalate and their lower alkyl esters, to such hydroxycarboxylic acid and lower alkyl esters thereof such as '-hydroxyethoxy yl benzoic acids, propane diols, 1, the 2-propane diols, 1, the 3-butanediol, 1, the 4-butanediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 5-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 1, the 4-cyclohexanedimethanol, terephthalyl alcohol, the ethylene oxide adduct of bisphenol-A, the ethylene oxide adduct of bisphenol S, triethylene glycol, polyoxyethylene glycol (polyethylene oxide glycol), polyoxy butylidene glycol (polytetraethylene oxide glycol), neopentyl glycol etc.
In addition, aromatic polyester can be with simple function compound such as benzoic acid, methoxyl group ployalkylene glycol for example the hydroxyl of end and/or part or all sealing of carboxyl to be formed, and perhaps can be that 3 such officials of glycerine, pentaerythrite etc. with for example minute quantity can above ester form compound modification in can obtaining the scope of the polymer of wire basically and form.
In addition, as the aromatic polyester among the present invention, can use with 2, the 6-(ethylene naphthalate) is other polyester beyond its of the following amount of aromatic polyester and a small amount of for example 20 weight % of main repetitive, for example the mixture that forms of blend such as PETG.
[polymerization catalyst, additive, stabilizing agent etc.]
(polymerization catalyst)
Aromatic polyester among the present invention is preferably made as polycondensation catalyst with the a kind of compound that is selected from zinc compound, antimonial, titanium compound, germanium compound and the manganese compound at least.By using this polycondensation catalyst, can easily the aromatic polyester among the present invention be adjusted to the excellent material of the transparency.
(additive, stabilizing agent)
In addition, among the present invention, above-mentioned aromatic polyester can contain additive as required, for example stabilizing agent, dyestuff, lubricant, ultra-violet absorber, fire retardant etc.For example, preferably contain inert particle with a small amount of ratio in order to give sliding to film.
As inert particle, preferred spherical silicon dioxide granule, preferred especially average grain diameter 0.05～1.6 μ m and size ratio (major diameter/minor axis) are 1.0～1.2 spherical silicon dioxide particulate.The pole of figure that this spherical silicon dioxide particulate is each particulate is spherical near ball, almost there is not oversize grain, and in the past to be used as (the ultramicrofine blocky particle about 10nm or their cohesion and the condensation product (aggregated particle) that forms about 0.5 μ m is significantly different of the known silicon dioxide microparticle of lubricant.
If the average grain diameter of spherical silicon dioxide particulate is greater than 1.6 μ m, the polymer film around the projection that the spherical silicon dioxide particulate forms is easy to generate crackle, and haze value increases easily, and is therefore not preferred.In addition, if less than 0.05 μ m, become poor, the reluctant film of sliding.Preferred 0.001～0.1 weight % of addition.If addition is more than 0.1 weight %, sliding is abundant, but the increase of the sum of crackle, the tendency that visible haze value increases, therefore not preferred.If be less than 0.001 weight %, become poor, the reluctant film of sliding.
(inherent viscosity of polymer (IV))
Adopt the PEN resin of the present invention that this method obtains also can section (pelletization), under the heating decompression or in the inert gas such as nitrogen, carry out solid phase.Finished pellet that solid phase is handled (contact with water, water vapour or the gas that contains water vapour behind the solid phase and obtain) with distilled water washing.By this washing the resin of fine powdery, palpus shape is removed.Generally speaking, be difficult to remove in the filtration operation of the melt extruding when membranization of such powdery, whiskers matter, molten resin, therefore enter in the film, become the quality shortcoming as inner foreign matter sometimes.Utilize solid phase, the oligomer that contains in the PEN resin is also reduced, the surperficial shortcoming that causes by oligomer that therefore can reduce further that face that the system film obtains exists.
The inherent viscosity of PEN resin of the present invention is 0.4～0.8dl/g, is preferably 0.45～0.75dl/g, is preferably 0.50～0.70dl/g especially.
Inherent viscosity is less than down in limited time, and the film after melt extruding becomes fragile, and has the problem that is easy to generate fracture when stretching.In addition, if the inherent viscosity of PEN resin surpasses the upper limit, for common synthetic gimmick, polymerization needs long-time, the productivity ratio variation.
PEN resin of the present invention normally will melt extrude after the pellet heated-air drying.Dry condition is to carry out more than 3 hours under 175 ℃ of the temperature of hot blast.Can reduce the amount of moisture that contains of pellet like this, prevent the reduction of the inherent viscosity that the hydrolysis when melt extruding produces.
[melt extruding film, the vertically manufacturing of monadic stretching membrane]
(melt extruding film)
Longitudinal uniaxial drawing polyethylene naphthalate polymer film of the present invention; can be by for example above-mentioned resin being extruded with the fusion sheet from I type mouth mould or T type mouth mould; chilling on cooler drum; form unstretching film, and then carry out uniaxial tension under the condition in projects reach the scope of membrane property of the present invention and make.
Among the present invention, the characteristic of the unstretching film of PEN is by melt extruding under about 300 ℃, makes the film driving fit cool off on cooler drum and obtain.For this adhesion method, can use known static driving fit method, fluid film be given the driving fit method of cooler drum face etc.In addition, also these adhesion methods only can be given the both ends of cooler drum of the width correspondence of the film that melt extrudes.The temperature of cooler drum is 20～70 ℃.Can access like this density little, do not have yet 3 direction of principal axis (extrude direction, with extrude the direction of direction quadrature and the thickness direction of a film) poly (ethylene naphthalate) film about equally of crystallization, refractive index basically.Among the present invention, preferably making 3 axial mean refractive indexs is 1.644～1.646, and density is 1.328～1.332g/cm
3If refractive index and density are outside these scopes, film is muddy or become fragile, and therefore is difficult to successfully carry out vertical uniaxial tension of subsequent processing.In addition, the not stretching poly (ethylene naphthalate) film that obtains, as the optical film purposes, preferably making birefringence n is below 0.003.In addition, if consider processabilities such as stretching, excipient, preferably making Tg is 120～130 ℃ scope.
The poly (ethylene naphthalate) film that do not stretch, its thickness is preferably 30～300 μ m, 80～200 μ m more preferably, its width is preferably 300～2000mm, more preferably 700～1600mm.
(the vertically manufacture method of monadic stretching membrane)
The preferred roller method of using stretches.Followingly the present invention is described in detail with reference to Fig. 1.Fig. 1 is the skeleton diagram of the part of the expression film forming apparatus that is used for vertical uniaxial tension of the present invention.
Vertical uniaxial tension device of the present invention roughly is made of 2 zones.The unstretching film of making in the preceding operation with 1. nip rolls binders, is sent into from the side (inlet) of sending into of film.The zone begins to form half (in advance) heating clambers before 2., 3. later half (longitudinal stretching) heating clamber from sending into side.The film that comes out from 3. later half (longitudinal stretching) heating clamber is with 4. nip rolls binders.2. preceding half (in advance) heating clamber and 3. later half (longitudinal stretching) heating clamber are separated by the next door.The temperature that forms the hot blast of half (in advance) heating clambers and 3. later half (longitudinal stretching) heating clamber before 2. all is controlled at width, film direction of travel ± 0.5 ℃ structure.Film is admitted to 1. nip rolls and the outlet side 4. nip rolls binders of side, applies tensile stress between these rollers.Nip rolls is made of metallic mirror surface roller and rubber nip rolls.
Among the present invention, its problem is the fold generation that obtains the film of high birefringence value and eliminate the film that takes place when stretching with uniform state by uniaxial tension.
In order to obtain corrugationless, poly (ethylene naphthalate) film that flatness is good with high orientation, the hot blast temperature of half (in advance) heating clamber 2, the hot blast temperature and the tensile stress of later half (longitudinal stretching) heating clamber 3 are fixed drawing point (not producing the phenomenons such as direction of travel swing of the drawing point of the film in the stretching at film) before must critically controlling in the space.
In order to improve birefringence, need to improve the stretching ratio of film, when improving stretching ratio, since because of (thickness distribution) in uneven thickness, the heating-up temperature of stretching cephacoria inhomogeneous etc., therefore drawing point also changes, and for drawing point (draw line) is not swung, uses the in uneven thickness little of the film that do not stretch, also little and uniform film such as degree of crystallinity, birefringence is critically controlled temperature and tension force and is stretched.
By drawing point is placed the space contact and phenomenons such as slip on roll surface owing to do not produce film, even so give high stretching ratio in order to manifest high Δ n, also can prevent to abrade, the generation of scuffing etc.
With unstretching film preheating in preceding half (in advance) heating clamber 2 of sending into, the temperature of this environment preferably than low about 40 ℃～10 ℃ temperature of glass transition temperature (Tg) of unstretching film, preferably sets at 90～110 ℃ particularly.Then, film is stretched at later half (longitudinal stretching) heating clamber 3 (distortion that produces essence).The temperature of this environment is preferably the scope of the pact (Tg-10)～(Tg+15) ℃ of unstretching film, is preferably set to 115 ℃～135 ℃ particularly.Setting preheat temperature and draft temperature like this, is because do not make the film in the stretching produce fold and the abundant birefringence value that improves film.That is, set by making preheat temperature and draft temperature have such scope, from the roughly initial place of later half (longitudinal stretching) heating clamber 3, promptly film has just entered 3 after-drawing of later half (longitudinal stretching) heating clamber and has begun.In addition, can access the film that the film that is stretched does not produce fold, flatness excellence in this case.If the film in stretching produces fold, then fully do not produce stretch orientation, the deterioration in uneven thickness of film as a result, the inhomogeneous increase that birefringence distributes in this part.
For the birefringence of poly (ethylene naphthalate) film of the present invention being brought up to the value of regulation, preferably must give 3.5～5.5 times stretching ratio.Stretching ratio can not be brought up to birefringence value desirable value during less than 3.5 times.In addition, when stretching ratio surpasses 5.5 times, can further improve birefringence, but the fold when stretching produces, be difficult to obtain even, smooth film.
Among the present invention, and then the speed of stretched film exerts an influence to the realization of high orientationization.Among the present invention, vertically the preferable range of uniaxial tension speed is 5～15 times/minute, and preferred scope is 5～10 times/minute.In addition, as mentioned above, vertically the preferred stretching ratio of uniaxial tension is 3.5～5.5 times, and preferred stretching ratio is 4.0～5.5 times.Preferred draw speed of the present invention is not merely determined by the velocity ratio of inlet nip rolls 1 and outlet nip rolls 4, but, represent with the ratio of stretching ratio with the summation of the stretching time of each fragment with stretching distance 100 five equilibriums of half (in advance) heating clambers and 3. later half (longitudinal stretching) heating clamber before 2..Their diagrammatic illustration is shown in Fig. 2.
That is,, 100 five equilibriums of stretching distance L (m) are cut apart distance be designated as [l=L/100], then use t (n)=l/V (n) expression for the stretching time t (min) of 1 fragment.
The outlet more little (becoming the short time) of the value of t approaching more later half (longitudinal stretching) heating clamber 3.
Stretching time T represents with the summation of t (1)～t (100), and the stretching ratio in the exit of later half (longitudinal stretching) heating clamber 3 is designated as B, and then draw speed Ev can be obtained by Ev=B/T (doubly/minute).
Find among the present invention, use has the roll-type stretching-machine of nip rolls 1, preceding half (in advance) heating clamber 2, later half (longitudinal stretching) heating clamber 3, nip rolls 4 successively from the inlet beginning, the temperature of preceding half (in advance) heating clamber 2 is set at 90～110 ℃, the temperature of later half (longitudinal stretching) heating clamber 3 is set at 115 ℃～135 ℃, the draw speed of later half (longitudinal stretching) heating clamber is set at 5～15 times/minute, scope with 3.5～5.5 times is given stretching ratio, can carry out vertical uniaxial tension of the poly (ethylene naphthalate) film of high orientation, homogeneous.
Nip rolls 1 and nip rolls 4 are preferably formed with thermal medium, electric heating and heat the structure that keeps uniform temperature internally.Have tension detector in the preferred nip rolls 4, detect the variation of tensile stress, the speed of the driven roller that is used to stretch with control.
Total light transmittance of longitudinal uniaxial drawing polyethylene naphthalate polymer film is more than 90%, to be preferably more than 91%.In addition, Δ n is 0.20～0.35 scope, preferred 0.25～0.33 scope.And then the angle of slow axis is below ± 1 °, preferred ± below 0.8 °.
Longitudinal uniaxial drawing polyethylene naphthalate polymer film, its thickness are 20～100 μ m, are preferably 30～100 μ m, and its width is 200～1000mm, is preferably 300～800mm.
The longitudinal uniaxial drawing polyethylene naphthalate polymer film that obtains from the productivity ratio aspect, is preferably made behind the film to be curled into the film winding laminate manufacturing of web-like.Further this winding laminate is cut, can form the narrower winding laminate of width.
The both ends that melt extrude the width of film are compared with the middle body of film, usually the thickness difference.Thickening is not tended at the film both ends when promptly carrying out edge traction (edge pinning), has carried out the edge and has tended to attenuation in the film both ends when pining down.Therefore, become desirable proterties, preferably before the film that curls, excise its two end portions (edge trimming) for the whole width at winding laminate makes the film proterties.
From the productivity ratio aspect, preferred film is batched wide the wanting greatly of film in the body, the scope of preferred 150～1000mm, the more preferably scope of 500～1000mm particularly.Have, when carrying out edge trimming, the wide value of these preferred films is interpreted as the value behind the edge trimming again.The length (film length) of curling can be by processing aspect, the decision of productivity ratio aspect, and there is no particular restriction, but the scope of 10～4000m is fit to.
The effect of invention
Make characteristic (copolymerization composition, the inherent viscosity) optimization of PEN, adopt to melt extrude legal system film unstretching film, then implement vertical uniaxial tension.Vertically during uniaxial tension, use the specific stretching device, condition (draft temperature, stretching ratio, tensile stress, draw speed) of wide region and optimization.The poly (ethylene naphthalate) film that obtains is a high birefringence, high transparent, and has the film on the excellent surface of corrugationless on the film.Vertical monadic stretching membrane of the present invention can use the base material film of mold release film to use with the adhesive of base material film, polarizing coating as the optical compensation material in the Novel LCD field, brings into play high-precision effect in blooming purposes field.
Embodiment
By the following examples the present invention is described in more detail.The present invention is not limited to these embodiment.Have, the various characteristics value of putting down in writing among the embodiment adopts assay method shown below to measure again.In addition, so-called film vertically, mean the direction of extruding when film is made, laterally so-called, mean in the face and the vertical direction of quadrature.
(inherent viscosity IV)
Use tetrachloroethanes: the mixed solvent of phenol=4: 6, under 35 ℃, measure.
(mensuration of the angle of length of delay, slow axis)
Use the automatic double refraction determining device KOBRA-21SDH of prince's instrumentation corporate system to measure.
Membrane sample is whole width, the length direction sampling 1000mm at width, and 5mm measures with measuring interval.Have, the length direction of film is taked sample from the 100mm inboard at the two ends of the central portion of distance film width and film width again, in mensuration.Measure delay and slow axis angle, resolve.
(birefringence)
Birefringence n is obtained by the delay Re calculating of obtaining from KOBRA-21SDH.Calculating formula is Re=Δ n * d, and wherein d uses the thickness of the film of measuring length of delay Re place.
(glass transition temperature Tg)
Use the system DSC of Seiko Electronics Industry Company (differential scanning calorimeter) 220 to measure.The condition determination of DSC is as follows.Test portion film 10mg is installed in the DSC device, heats for 20 ℃/minute with programming rate, after fusion under 300 ℃ the temperature, chilling in liquid nitrogen.With 10 ℃/minute this chilling test portion is heated up, detect glass transition temperature.
(refractive index)
Use Abbe formula refractometer, use sodium D-line (589nm), contact liquid uses the mixture of diiodomethane or diiodomethane and sulphur, under 23 ℃, 65%RH, measure a direction in the face refractive index n x (for example film refractive index n MD) longitudinally and with the refractive index n y (for example horizontal refractive index n TD of film) of the direction of its quadrature.
(density)
With the density gradient column that has used calcium nitrate aqueous solution, adopt the method for drifting along to measure down at 25 ℃.
(total light transmittance)
According to the method for putting down in writing among the JIS K6714-1958, use the HR-100 type haze meter of color technical research institute system in the village, measure total light transmittance Tt% of the membrane sample under the visible light.
(thickness and in uneven thickness)
Thickness: use the electronic gauge (K-312A type) of ANRITSU corporate system, press 30g to measure film thickness with pin.
In uneven thickness: as on the orthogonal direction in face (for example vertical and horizontal of film), to use the electronic gauge (K-312 type) of ANRITSU corporate system,, obtain in uneven thickness by following formula with the film thickness of the long 100mm of pin pressure 30g METHOD FOR CONTINUOUS DETERMINATION.
The minimum of a value (μ m) of the maximum of (μ m)=thickness in uneven thickness (μ m)-thickness
Embodiments of the invention, comparative example are shown in embodiment 1～3, the comparative example 1～3 of table 1.
Adopt conventional method to obtain gathering 2,6-(ethylene naphthalate) composition is the resin of 95 moles of %.And then adopt known method to make its solid phase, and make inherent viscosity IV rise to 0.65, what obtained high polymerization degree gathers 2,6-(ethylene naphthalate) pellet.175 ℃ down with granular resin heated-air drying after 5 hours, with melt extruding machine, be expressed into by I type mouth mould on 60 ℃ the cooler drum 300 ℃ of following fusions, employing static driving fit method cooling curing has obtained unstretching film (thickness 150 μ m and thickness 80 μ m).
The characteristic of the unstretching film that obtains is as follows: inherent viscosity IV is 0.62, and birefringence n is that 0.003,3 axial refractive index is 1.645, and density is 1.330g/cm
3, glass transition temperature Tg is 123 ℃.Film is that homogeneous is transparent.
In vertical uniaxial tension,, used the film of thick 150 μ m, wide 780mm as unstretching film (undressed).Use the roll-type longitudinal stretching machine shown in Fig. 1, the temperature of preceding half (in advance) heating clamber 2 is set at 100 ℃, and the temperature of later half (longitudinal stretching) heating clamber 3 is set at 126 ℃, under the condition of 5.03 times of stretching ratios, 7.0 times/minute of draw speeds, stretch.The entrance velocity of film is 2m/ minute.Film thickness after the stretching is 65 μ m, and the film width is 345mm, and in uneven thickness and original base material is compared, and the absolute value of deviation reduces.In addition, total light transmittance is 91%.
Having obtained birefringence n is 0.320, and the angle of slow axis is vertical monadic stretching membrane of 0.8～-0.8 ° high birefringence.In this film, do not produce fold fully. postponing (Re) is 20, and 800nm as phase retardation film, is the extremely high film of its phase difference value.
Use the unstretching film of thick 80 μ m, wide 480mm, under 5.00 times of 126 ℃ of draft temperatures, stretching ratio, other conditions are identical with embodiment 1, stretch.Film thickness after the stretching is 33 μ m, and total light transmittance is 91%.
Film is wide to be 225mm.Having obtained birefringence n is 0.321, and the angle of slow axis is 0.6～-0.6 ° a stretched film.Re is 10,600nm.Do not observe fold fully.
Except the temperature of later half (longitudinal stretching) heating clamber 3 being reduced by 7 ℃ and be made as 119 ℃, under the condition identical, stretch with embodiment 2.Film thickness after the stretching is 33 μ m, and total light transmittance is 92%.
Δ n is 0.315 (angle of slow axis is 0.6～-0.6 °), slightly reduces, but has obtained the film of the sufficient high birefringence value of having of corrugationless.(Re＝10,400nm)。
Use the unstretching film of thick 80 μ m, wide 1480mm, under 7.0 times/minute of 119 ℃ of draft temperatures, 5.00 times of stretching ratios, draw speed, carry out vertical uniaxial tension similarly to Example 1.Film thickness after the stretching is 33 μ m, and wide is 695mm, and total light transmittance is 92%.
Δ n is 0.315, and the angle of slow axis is 0.6～-0.6 °.This film does not produce fold.
Comparative example 1～3
Use the unstretching film of thick 80 μ m, wide 480mm, under 3.5 times/minute of 125 ℃ of draft temperatures, 5.00 times of stretching ratios, draw speed, stretch, obtained vertical monadic stretching membrane of comparative example 1.
In addition, use same stretched film, under 4.1 times/minute of 120 ℃ of draft temperatures, 5.00 times of stretching ratios, draw speed, stretch, obtained vertical monadic stretching membrane of comparative example 2.
The birefringence n of two comparative examples is all near 0.30, and is very high, but produced the part fold, is unaccommodated as blooming.
In addition, use same unstretching film, in comparative example 3, draft temperature is reduced to 115 ℃, under 3.5 times/minute of draw speeds, stretch.Can access the vertical monadic stretching membrane that does not produce fold this moment.But stretching ratio can only be brought up to 2.20 times, and birefringence n is low to reach 0.150.Under the situation of comparative example, vertically monadic stretching membrane is in uneven thickness all greatly to more than the 4 μ m, and compares below the 3 μ m of the film of embodiment 1～4, obviously worsens.
Table 1
Claims (3)
1. longitudinal uniaxial drawing polyethylene naphthalate polymer film, it is characterized in that: the not stretching poly (ethylene naphthalate) film that is formed at the PEN resin of 0.4～0.8dl/g scope by inherent viscosity is carried out vertical uniaxial tension and obtains, total light transmittance is more than 90%, the refractive index n x of draw direction and with the difference Δ n of the refractive index n y of the width of its quadrature be 0.25～0.35, the angle of slow axis is below ± 1 °, thickness after the stretching is 20～100 μ m, and film is wide to be the scope of 200～1000mm.
2. longitudinal uniaxial drawing polyethylene naphthalate polymer film according to claim 1, wherein, poly-2 of poly (ethylene naphthalate) film does not stretch, the copolymerization ratio of 6-(ethylene naphthalate) is 80 moles more than the %, birefringence n is below 0.003, Tg is 120～130 ℃, and refractive index is 1.644～1.646, and density is 1.328～1.332g/cm
3, thickness is 30～300 μ m, width is 300～2000mm.
3. the manufacture method of the described longitudinal uniaxial drawing polyethylene naphthalate polymer film of claim 1, it is characterized in that: use from the inlet beginning to have nip rolls successively, preceding half (in advance) heating clamber, later half (longitudinal stretching) heating clamber, the roll-type longitudinal stretching machine of nip rolls, the temperature of preceding half (in advance) heating clamber is set at 90～110 ℃, the temperature of later half (longitudinal stretching) heating clamber is set at 115 ℃～135 ℃, the draw speed of later half (longitudinal stretching) heating clamber is set at 5～15 times/minute, give 3.5～5.5 times stretching ratio, half (in advance) heating clamber is meant and is used for pre-warmed preceding false add hot cell before wherein said, and described later half (longitudinal stretching) heating clamber is meant the later half heating clamber that is used for longitudinal stretching.
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| CN104950368A (en) * | 2014-03-31 | 2015-09-30 | 日东电工株式会社 | Stretch lamination body making method, stretch lamination body, polarizing film and making method thereof |
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| WO2004113043A3 (en) * | 2003-06-17 | 2005-11-17 | Mitsubishi Polyester Film Llc | Propane diol-based polyester resin and shrink film |
| WO2006051884A1 (en) * | 2004-11-10 | 2006-05-18 | Mitsubishi Plastics, Inc. | Heat shrinkable laminated film, molded article using such film, and heat shrinkable label and container |
| CN101052902A (en) * | 2004-10-29 | 2007-10-10 | 3M创新有限公司 | Optical bodies and methods for making optical bodies |
| CN101180554A (en) * | 2005-04-08 | 2008-05-14 | 3M创新有限公司 | Heat setting optical films |
| JP4582370B2 (en) * | 2000-06-27 | 2010-11-17 | 東洋紡績株式会社 | Method for producing optically easy-adhesive film |
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2008
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| EP0225630A2 (en) * | 1985-12-09 | 1987-06-16 | Diafoil Hoechst Co., Ltd | Uniaxially high-oriented polyethylene naphthalate film for liquid crystal panel substrates |
| JP4582370B2 (en) * | 2000-06-27 | 2010-11-17 | 東洋紡績株式会社 | Method for producing optically easy-adhesive film |
| WO2004113043A3 (en) * | 2003-06-17 | 2005-11-17 | Mitsubishi Polyester Film Llc | Propane diol-based polyester resin and shrink film |
| CN101052902A (en) * | 2004-10-29 | 2007-10-10 | 3M创新有限公司 | Optical bodies and methods for making optical bodies |
| WO2006051884A1 (en) * | 2004-11-10 | 2006-05-18 | Mitsubishi Plastics, Inc. | Heat shrinkable laminated film, molded article using such film, and heat shrinkable label and container |
| CN101180554A (en) * | 2005-04-08 | 2008-05-14 | 3M创新有限公司 | Heat setting optical films |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104950368A (en) * | 2014-03-31 | 2015-09-30 | 日东电工株式会社 | Stretch lamination body making method, stretch lamination body, polarizing film and making method thereof |
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