CN101205307B - Single layer or multilayer, stabilised polyester film - Google Patents

Single layer or multilayer, stabilised polyester film Download PDF

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Publication number
CN101205307B
CN101205307B CN2007101999003A CN200710199900A CN101205307B CN 101205307 B CN101205307 B CN 101205307B CN 2007101999003 A CN2007101999003 A CN 2007101999003A CN 200710199900 A CN200710199900 A CN 200710199900A CN 101205307 B CN101205307 B CN 101205307B
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Prior art keywords
film
polyester film
stabilizer
alkyl
layer
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CN101205307A (en
Inventor
H·克利施
U·穆沙尔
I·菲舍尔
M·耶斯贝格尔
L·博特
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Mitsubishi Polyester Film GmbH
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Mitsubishi Polyester Film GmbH
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Priority claimed from DE200710001443 external-priority patent/DE102007001443A1/en
Priority claimed from DE102007045581A external-priority patent/DE102007045581A1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0044—Stabilisers, e.g. against oxydation, light or heat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Abstract

Biaxially oriented mono- or multilayered polyester film contains at least one UV stabilizer according to formula (I): wherein R1 is -H, C1-C12-alkyl, -aryl, -S-(C1-C12)-alkyl or -O-R9 or -O-(C1-C5)-alkylene-C(O)O-R9, wherein R9 is -aryl or C1-C12-alkyl, R3 and R4 and R2, R5, R6, R7 and R8 independently from each other represent -H, -(C1-C12)-alkyl, -O-(C1-C12)-alkyl, -aryl or -O-aryl, wherein said alkyl radicals with more than two C-atoms and alkylene radicals with more than one C-atom can be linear or branched.

Description

The stabilised polyester film of single or multiple lift
The present invention relates to single or multiple lift polyester film to ultraviolet light stabilized.The invention further relates to method of this film of preparation and uses thereof.
The known UV stablizer great majority that are used for polymkeric substance are derived from the material group of triazine, phentriazine, UVNUL MS-40, bulky amine (HALS=hindered amine as light stabilizer) and many other types.Can for example in DE-A-10135795, find it to enumerate.The oriented polyester film of UV stable also is known and also discloses the given activity of the stablizer that is derived from the triazine group that is used for alignment films (referring to for example WO98/06575).
WO98/06575 also points out the variable suitability in the triazine group; And (=2-(4 to point out especially suitable commercially available Tinuvin
Figure 2007101999003_0
1577; 6-phenylbenzene-1,3,5-triazines-2-yl)-5-(hexyl)-oxygen base phenol; By Ciba SC, CH makes).
In addition, DE-A-10135795 discloses the difference in the triazine group and has proposed many purposes new and known triazine that are used for film.This document is also mentioned polyester film, yet, only make instance to polyolefin film.Having that the unitary further triazine of biphenyl is disclosed is that suitable (compound a of giving an example/b/c/d/e/f/g) is with to disclose commercially available Tinuvin
Figure 2007101999003_1
1577 (compound j) especially suitable.In addition, considered and other UV stabilizers, especially be derived from the binding substances of the compound in the HALS group.Because possible number change, the sum of the potential suitable stabilizers of therefore in chemical formula, mentioning reaches thousands of kinds.It is not feasible transferring to (especially aromatics) polyester from polyolefine, because uv-absorbing is different fully with processing conditions, so stablizer must have corresponding other performances.
DE-A-10135795 and WO98/06575 mention Tinuvin
Figure 2007101999003_2
the 1577th, especially suitable and preferred stablizer.
Although Tinuvin 1577 has advantage; But it has significant disadvantage, particularly in the processing of oriented polyester film.In melt; Be similar to other non-polymer UV stabilizers, Tinuvin
Figure 2007101999003_4
1577 does not make contributions to total viscosity.Because it must be the consumption interpolation of 1-5wt% with the scope; For the ultraviolet stability of realizing class of trade (under the weather condition of European center weather minimum 5 years usually respectively; Be the life-span in 2 years in the Florida test), the remarkable decline of viscosity appears in the production of film.These decline right and wrong are required, and cause that film is broken, striped and other make trouble.In addition, use triaizine compounds to cause the smell that many people of letting feel put about.And; Triaizine compounds; For example Tinuvin
Figure 2007101999003_5
1577 has residual absorbancy in visible spectrum range, and this will cause the film flavescence.
The objective of the invention is to overcome above-mentioned shortcoming and the polyester film with ultraviolet stability is provided, its ultraviolet stability is the same good with the film that contains Tinuvin
Figure 2007101999003_6
1577 at least; Especially for this performance, they should be superior to containing the polyester film of Tinuvin 1577.In the present invention, be superior to being meant under lower concentration level, to the same long or longer stability of ultraviolet ray.Except tangible economic advantages, the level of low concentration provides significant technical superiority.
Through using UV stabilizer, realize the object of the invention according to following formula (I):
Figure S2007101999003D00021
Wherein:
R 1Be-H ,-the C1-C12 alkyl ,-aryl ,-S-(C1-C12) alkyl or-O-R 9Or-O-(C1-C5)-alkylidene group-C (O) O-R 9, wherein
R 9Be-aryl or-the C1-C12 alkyl,
R 3And R 4Be
Figure S2007101999003D00022
With
R 2, R 5, R 6, R 7And R 8Independently of one another expression-H ,-(C1-C12)-alkyl ,-O-(C1-C12)-alkyl ,-aryl ,-the O-aryl,
The wherein said alkyl that has greater than two carbon atoms can be a straight or branched with the alkylidene group that has greater than a carbon atom.
Preferably according to the compound of formula (I), wherein
R 1Be-O-R 9Or-O-CH (CH 3)-C (O) O-R 9, wherein
R 9Represent hexyl, heptyl or octyl group and
R 2, R 5, R 6, R 7And R 8Expression-H.
Especially preferably according to the compound of formula (I), wherein
R 1Be-O-R 9, wherein
R 9Be octyl group, preferred particularly 2-ethylhexyl and
R 2, R 5, R 6, R 7And R 8Expression-H.
Also especially preferably according to the compound of formula (I), wherein
R 1Be-O-CH (CH 3)-C (O) O-R 9, wherein
R 9Represent octyl group with
R 2, R 5, R 6, R 7And R 8Expression-H.
Aryl is meant unsubstituted single or many OH, Cl, Br, I, NO 2, NH 2, SO 3H, COOH, C1-C4-alkyl or the substituted phenyl of C1-C4-alkoxyl group, pyridyl, naphthyl, 2,3-indanyl or indenyl, preferred phenyl, especially preferred unsubstituted phenyl.
Especially preferred:
The 2-that Ciba SC (CH) provides with title Tinuvin
Figure 2007101999003_8
479 (2-hydroxyl-4-[1-carbonyl octyloxy oxyethyl group] phenyl)-4; Two (the 4-phenyl)-1 of 6-; 3, the 5-triazine.
Figure S2007101999003D00031
Also preferably according to the compound of formula (II):
Figure S2007101999003D00041
Be added in an amount of 0.1-10wt%, the said UV stabilizer of preferred 0.25-4wt% and especially preferred 0.4-2.5wt%.
Particularly preferred compounds using Tinuvin
Figure 2007101999003_9
479 and / or according to formula (II) the compound of Tinuvin
Figure 2007101999003_10
1577 - half the amount in the case to get the same UV stability.
The weight percentage of below mentioning is meant the quality of each layer that contains said compound.
Polymkeric substance in the film in B of basic unit and the remainder layer (not considering other additives that UV stabilizer and hereinafter are mentioned) preferably is made up of 80wt% thermoplastic polyester at least.Suitable polyester especially comprise by the preparation of terepthaloyl moietie and terephthalic acid those (=polyethyleneterephthalate, PET), by terepthaloyl moietie and naphthalene-2, the 6-dicarboxylicacid prepare those (=gather 2; 6-naphthalic acid second diester, PEN), by 1; Those of two methylol hexanaphthenes of 4-and terephthalic acid preparation (=gather (terephthalic acid-1,4-hexamethylene two methylene esters, PCDT); With by terepthaloyl moietie, naphthalene-2,6-dicarboxylicacid and biphenyl-4, those of 4`-dicarboxylicacid preparation (=gather 2; The two phenylformic acid second diester of 6-naphthalic acid, PENBB) with by the polyester of m-phthalic acid and ethylene glycol, and any mixture of said carboxylic acid and glycol.Especially preferably by 90mol% at least, 95mol% terepthaloyl moietie unit and terephthalic acid units or terepthaloyl moietie unit and naphthalene-2 especially at least, the polyester of 6-dicarboxylic acid units preparation.All the other monomeric units are derived from other aliphatic series, alicyclic or aromatic diol and/or dicarboxylicacid.
Other suitable aliphatic diols for example are glycol ether, triglycol, general formula HO-(CH 2) nThe aliphatic diol of-OH, wherein n is 1 to preferably less than 10.
In addition, membrane polymer can contain other polymkeric substance of maximum 20wt%, for example polyolefine (for example, cyclic olefin polymer, Vestolen PP 7052 etc.), polymeric amide or polyetherimide.Preferably, its consumption less than 10wt% and especially preferred polymers form by the aforementioned polyester of 100wt%.
Film can contain common additive, for example stablizer and/or anti in addition.Preferably in the skin (A and C layer) of multilayer film (ABC, B=basic unit), use anti.The instance of employed stablizer is a phosphorus compound, for example phosphoric acid or SULPHOSUCCINIC ACID ESTER.Further the instance of additive be free-radical scavengers/thermo-stabilizer (for example; Irganox
Figure 2007101999003_11
, preferred Irganox 1010).
Typical anti is inorganic and/or organic granular, for example lime carbonate, crystallization or soft silica (SiO 2), calcium, barium, zinc or the magnesium salts of talcum, magnesiumcarbonate, barium carbonate, calcium sulfate, permanent white, Trilithium phosphate, calcium phosphate, trimagnesium phosphate, aluminum oxide, pure aluminium silicate, lithium fluoride, employed dicarboxylicacid, titanium oxide, kaolin or crosslinked granules of polystyrene, PMMA particle or acrylate particles.
Spendable other antis are mixture or same composition but mixtures of varigrained anti of two kinds or more kinds of different preventing adhesion agents.Can anti be joined in the independent layer with favourable separately consumption, for example the dispersion-s form with divalent alcohol perhaps adds by the master batch form in extrusion in polycondensation process.Typically, the consumption of anti is no more than 5wt%, preferably is no more than 1wt%, and white pigment, and for example the consumption of titanium oxide is no more than 20wt%.
Except UV stabilizer of the present invention, can optionally use consumption preferably less than 2wt% and especially preferred other UV stabilizers (for example other triazines, UVNUL MS-40 etc.) (selecting with reference to DE-A-10135795 the 8th page the 2nd) less than 0.5wt%.The compound (hindered amine light stabilizer is referring to DE-A-10135795) that is derived from the HALS group proves disadvantageous.Opposite with the long lifetime of the PP film described in the embodiment 7 of DE-A-10135795, in polyester film, use the HALS stablizer not have significant prolongation measured life-span under ultraviolet radiation; In addition, in the Weather process, flavescence and similarly after 500 hours, occurs, when reclaiming (reclaim) film, significant flavescence occurred.
In the most preferred embodiment of the present invention, except according to of the present invention those stablizer, do not use extra stablizer.
In a preferred embodiment of the invention, with 0.01-1wt%, more preferably the free-radical scavengers of 0.01-0.1wt% (inhibitor) joins one deck of film or more in the multilayer.In order to select free-radical scavengers (inhibitor), with reference to DE-A-10135795, the 7th page the 1st.Be proved to be especially suitable available from Irganox
Figure 2007101999003_13
1010 (CAS-No.6683-19-8) of Ciba SC (CH) or stablizer with CAS-No.065140-91-2.
In another embodiment preferred of the present invention, make film have flame retardant resistance.As combustion stabilizer, preferably be given in soluble organo phosphorous compounds in the polyester.Especially preferably be incorporated into polyester intrachain phosphorus compound and especially preferably wherein phosphorus atom be positioned at the side intrachain those.Can be incorporated into this examples for compounds of polyester intrachain is the ester with CAS-No.63562-34-5.Typically add fire retardant, the feasible content sum from phosphorus in the fire retardant of its consumption is 0.1-2wt%.
According to the present invention, the total thickness of polyester film is the 1-500 micron, especially 10-50 micron and preferred 12-30 micron.
Film has one deck that all above-mentioned additives can be independently of one another share therein or multilayer more.In multilayer film, prove advantageously when outside exposure layer (or under the situation of bilateral exposure and trilamellar membrane at least, two outer layers) and contain the UV stabilizer of Duoing than one or more layers nexine.
Economic and technical especially advantageous embodiment is the film that has greater than two-layer; Wherein greater than 25%; Be preferably greater than 30%; Especially be preferably greater than 35% UV stabilizer and be included in the skin and especially preferred one deck skin contains greater than 25%, be preferably greater than 30% and especially be preferably greater than 35% stablizer.
Proof advantageously in each layer the consumption of UV stabilizer be no more than 7wt%; Preferred each layer do not contain the UV stabilizer greater than 5wt%; This is because the percent crystallinity increase of stretching induction can reduce the solubleness of UV stabilizer in polyester matrix, and this can cause UV stabilizer to ooze out.Prove Tinuvin
Figure 2007101999003_14
the 479th here, favourable, because it is obviously with polyester matrix reaction and formation covalent linkage and demonstrate especially low mobility.
In the multiwalled embodiment, prove advantageously at least a two-layer UV stabilizer that contains towards incident light.Preferably the consumption of UV stabilizer should be not less than 0.1wt% in this is two-layer.In transparent embodiment (transparency＞50%), prove that all layers of advantageously working as film contain the UV stabilizer of 0.1wt% at least.
When the rete towards light contains less than 4wt% mean particle size d 50Greater than the white pigment of 200nm (TiO for example 2, BaSO 4, CaCO 3Deng) time, prove advantageously outer UV stabilizer and the especially preferred UV stabilizer of 1.0wt% at least of 0.75wt% at least of containing.
In preferred embodiments, film of the present invention demonstrates the vertical and horizontal shrinking percentage less than 10% under 200 ℃, preferably less than 6% with especially preferably less than 4%.In addition, under 100 ℃, this film demonstrates the expansion less than 3%, preferably less than 1% with especially preferably less than 0.3%.Can for example before rolling, relax, realize this dimensional stability (referring to process explanation) through the suitable of film.
In preferred embodiments, film also demonstrates greater than 3000N/mm on vertical and horizontal 2Young's modulus, be preferably greater than 3500N/mm 2And especially preferably＞4100N/mm 2In the F5 parameter on the vertical and horizontal (power under 5% elongation) preferable range greater than 80N/mm 2Be preferably greater than 90N/mm 2Can be for example suitable biaxial stretch-formed these mechanical propertys (referring to process explanation) that obtain through film.
Said shrinking percentage and mechanical property advantageously influence in ultraviolet ageing and other weather conditions, for example the weather resistance of film under heat and the moisture.
In a further preferred embodiment, at least one side with the adhesive coated film for printing color.Suitable coating for example is propenoate or the copolyesters of sulfoisophthalic acid content greater than 0.2wt%.
Technology
By dicarboxylicacid and terepthaloyl moietie is initial (so-called " PTA " method), and perhaps by the ester of dicarboxylicacid, preferred dimethyl ester and terepthaloyl moietie are initial (so-called " DMT " method), obtain the polyester matrix polymkeric substance of each layer through polycondensation.The SV value preferable range of available polyethyleneterephthalate is 600-900 and gathers 2 that 6-naphthalic acid second diester is about 500-800.
If exist, can in the manufacturing processed of polyester, add particle.For this reason with particles dispersed in terepthaloyl moietie, randomly pulverizing, decantation etc., and or esterification (exchange) or condensation polymerization step in joining in the reactor drum.In preferred replacement scheme, adopt prepared in twin-screw extruder to contain the concentrated polyester master batch of particle or additive, and in the extrusion of film, dilute with not containing the particulate polyester.In the extrusion of this external film, can directly add particle and additive in twin screw extruder.
Perhaps the noncrosslinking organic granular of processing in twin screw extruder prepares master batch, perhaps directly in the extrusion of film, adds.
Can UV stabilizer be joined in the film by masterbatch technique.For this reason, in twin screw extruder, plastify polyester raw material, and add UV stabilizer.Subsequently through interior and quencher and the granulation of hole extrusioning mixture to water-bath.When master batch contains consumption is 1-33wt%, during the UV stabilizer of preferred 5-25wt% and especially preferred 10-20wt%, proves favourable.The consumption that is lower than this scope is quite uneconomical, and is higher than 25wt%, and then the bonding of UV stabilizer in polyester matrix becomes not enough, causes significant " oozing out " under the numerical value of 33wt% being higher than.
Can in the production process of film, directly add UV stabilizer.Stablizer with various consumptions directly is metered in the forcing machine for this reason.Yet during many when using (two at least) screw extrusion press, this only obtains good distribution results.
In addition; Proof advantageously uses layer of inert (for example nitrogen or argon gas) to cover the inlet of forcing machine; This be because the producing apparatus place of film directly extrude and production at master batch in, UV stabilizer of the present invention is responsive to the oxidation stress that high extrusion temperature causes.
When using single screw extrusion machine, prove advantageously predrying polyester.Under the situation of twin screw extruder, can save drying step with degas zone.
At first, the polymkeric substance or the polymeric blends of the difference layer under compression and plasticizing layer or the multilayer film situation in forcing machine.By the single or multiple lift nozzle, be flat film melt then, be pressed through seam die (wide seam type nozzle) and, thereby cause film cooling and sclerosis by chill roll and the traction of one or more pull roll with melt forming.
Diaxial orientation, promptly biaxial stretch-formed film of the present invention.Usually carry out the biaxial stretch-formed of film according to the order of sequence.Preferably at first machine-direction oriented (i.e. vertical=MD direction), horizontal orientation (i.e.=TD direction vertical) then with vertically.Can be that the two rollers that turn round under the friction-motion speed (corresponding to required stretch ratio) carry out longitudinal stretching under auxiliary.
For cross directional stretch, use suitable tentering framework usually.
With stretch differently according to the order of sequence, it is possible stretching simultaneously, but does not necessarily require.
Temperature when stretching can change in the wide region relatively, and depends on the performance that film is required.Usually,, scope carries out longitudinal stretching and be that 90 ℃ (beginning stretches) are carried out cross directional stretch in the TR of 140 ℃ (stretch and stop) under being 80-130 ℃ temperature (80-130 ℃ Heating temperature) in scope.Longitudinal stretching is 2.0: 1 to 5.5: 1 than scope, preferred 2.2: 1 to 5.0: 1.Cross directional stretch is than usually in 2.4: 1 to 5.0: 1 scopes, preferred 2.6: 1 to 4.5: 1.
In order to obtain required film properties, prove that advantageously draft temperature (MD and TD direction) is lower than 125 ℃ and preferably be lower than 118 ℃.
Before cross directional stretch, the online coating of currently known methods can be passed through in one or two surface of film.As an example, online coating can cause the binding property of metal level or printing-ink to improve the perhaps improvement of antistatic property or processing characteristics.When the coextrusion layer of outside does not contain the particle that improves smooth and curved characteristic, can locate to apply to contain the particulate coating in this stage.
In heat setting type process subsequently, in time period of keep film under 150-250 ℃ the temperature under tensioning about 0.1-10 second with in order to obtain preferred shrinking percentage value, transverse relaxation at least 1%, preferably at least 3% and especially preferably at least 4%.Preferably, scope relaxes under being 150-190 ℃ temperature.Preferably less than 25% with greater than 5% whole lax occurring at first in time of relaxation of 25%.The film of reeling routinely then.
In the production process of film, guarantee under the situation of physics that does not have remarkable negative impact film and optical property, can introduce again Recycled materials again in expressing technique with the consumption of 20-60wt% with respect to the gross weight of film.
Film of the present invention demonstrates very good ultraviolet stability, low inherent colour; And compare with Tinuvin
Figure 2007101999003_15
1577; Under identical ultraviolet stability, reduce the content of UV stabilizer, and the smell that is reduced in the film manufacturing processed stimulates.In addition, shown, therefore when between UV stable and non-stable film type, back and forth changing, can be reduced in the die pressure that occurs in the film manufacturing processed and change, so that it is broken when switching, to observe less film because the content of novel stabilizer is lower.
Use following TP to characterize starting material and film:
Median diameter d 50Measurement
By laser, on Horiba LA50, use laser diffraction (other surveying instruments for example are Malvern Master Sizer or Sympathec Helos, and they utilize identical measuring principle) to measure median diameter d 50For this reason, in Xiao Chi (cuvette), place sample and water together, then it is installed in the metering facility.By this dispersion-s of laser scanning, and pass through relatively this signal and calibration curve, measure size-grade distribution.Size-grade distribution is characterised in that two parameter: intermediate value d 50(measuring of=MV) and variance, so-called SPAN98 (measuring of=particle diameter variance).Measuring operation is to comprise mathematics mensuration d automatically and also 50Value.According to definition,, measure the d here by " relatively " cumulative grain-size distribution curve 50Value.On axis of abscissa, obtain required d in the point of crossing of 50% ordinate value on the summation curve (intersection) 50Value.
Nanoparticles (eg Aerosil
Figure 2007101999003_16
and Nyacol
Figure 2007101999003_17
) of the primary particle size
By research particulate transmission electron microscopy (TEM) image, measure the mean sizes of primary granule.When with film or particle form sampling, use the section of slicing machine to carry out the TEM inspection.
Transparency
Measure transparency according to ASTM-D 1033-77.
SV value (normal viscosity)
According to DIN 53726, in dichloro acetic acid (DCA), measurement standard viscosity SV under the concentration of 1wt%.Be described below according to relative viscosity (η Relatively) the nondimensional SV value of mensuration:
SV=(η Relatively-1) * 1000
Relation is as follows between intrinsic viscosity (IV) and the normal viscosity:
IV[η]＝6.907×10 -4SV(DCA)+0.063096[dl/g]
Mechanical property
Based on DIN EN ISO 572-1 and-3, use the rectangular of the film be of a size of 100mm * 15mm, measure mechanical property.By lateral position sensor, measure length variations.Under the draw rate of 10%/min,, measure Young's modulus as the slope of 0.2 to 0.3 elongation (extension).Under the draw rate of 100%/min, measure σ 5-value (power under 5% elongation).
Shrinking percentage
Use the square membrane sample of side width, measure percent thermal shrinkage as 10cm.Measure sample (side edge length L accurately 0), indoor at the forced convection drying chamber, annealed 15 minutes down at 200 ℃, at room temperature accurately measure then (side edge length L).Obtain shrinking percentage by following equation.
Shrinking percentage [%]=100 (L 0-L)/L 0
Ultraviolet stability
Described in the 8th page of DE-A-69731750 (DE WO98/06575 of the same clan), measure ultraviolet stability, and provide the UTS value with the percentage ratio form of initial value.About the Weather time, the embodiment that mentions below the reference.
Smell aborning stimulates
Because it is subjective that smell stimulates, therefore after 30 minutes PT, inquire 10 its sense of smell of direct labor individually.Each workman must be based on grade 1-4 (referring to following) evaluation smell.Add with oder levels and divided by workman's quantity with the MV presented.Grade point:
1 compares with the polyester film production of " normally ", does not have extra sense of smell
2 light additional odor are felt (not stimulating)
3 significant significantly smells (stimulation)
The additional odor (very annoying/as to make us unhappy) that semi-finals is strong
Embodiment
Comparative Examples 1
Repeat the embodiment 1 of DE-A-69731750 (DE WO98/06575 of the same clan), comprising following difference:
Owing to do not have 6 micron silica particulate starting material, therefore use 1.1wt%Silysia
Figure 2007101999003_18
The silicon-dioxide of 440 types (available from Fuji Silysia, Japan, its d 50Be about 4.4 microns).Be used for can not sealing ply the polyethyleneterephthalate starting material (IPA content is 0.05wt%; Glycol ether 0.7wt%) contains 1wt%Tinuvin
Figure 2007101999003_19
1577 (Ciba SC, Sweden).By the master batch of forming by the Tinuvin
Figure 2007101999003_20
1577 of 10wt% in PET, add Tinuvin
Figure 2007101999003_21
.
Be described below and carry out heat setting type:
Heat setting type Temperature 225-150 ℃
Time length 2 s
Relaxing on 200-150 ℃ of following TD direction 3 ％
Oder levels is 2.5.
In case switch to this film type, the slight pressure of observing in die head changes.After 1000 hours Weather, tensile strength (UTS) value is 69% of initial value.
Embodiment 1
Be similar to Comparative Examples 1; But use 0.5wt%Tinuvin 479 (Ciba SC, CH).
Oder levels is 1.4.
In case switch to this film type, observing does not have pressure change in the die head.Tensile strength values after 1000 hours Weather (UTS) is 74% of an initial value.
Embodiment 2
Be similar to embodiment 1; But use 1.0wt%Tinuvin 479 (Ciba SC, CH).
In case switch to this film type, observe pressure change small in the die head.
Oder levels is 1.8.
Tensile strength values after 1000 hours Weather (UTS) is 89% of an initial value.
Embodiment 3
Manufacturing thickness is 20 microns trilamellar membrane.
It is interior also through the seam die that polymeric blends is fed into pin hole (pinole) (geat cover) together, and electrostatic precipitation is on the chill roll that is maintained under 60 ℃.Then under following condition, vertically, cross directional stretch film then:
Longitudinal stretching Heating temperature 75-115 ℃
Draft temperature 115 ℃
The longitudinal stretching ratio 3.7
Cross directional stretch Heating temperature 100 ℃
Draft temperature 110 ℃
The cross directional stretch ratio 4.0
Heat setting type Temperature 237-150 ℃
Time length 2 s
Under 200-150 ℃, relaxing on TD 7 ％
In three-screw extruder, plastify three kinds of polymeric blends down at 290 ℃:
1.70wt% has 0.1wt%SiO 2Silysia
Figure 2007101999003_24
340 (Fuji Silysia, SV value JP) is that 800 polyethyleneterephthalate and 30wt%SV value are 700 and Tinuvin
Figure 2007101999003_25
479 content are polyethyleneterephthalate master batch → A layer of 20wt%
The 2.98wt%SV value be 800 polyethyleneterephthalate and 2wt%SV value be 700 and Tinuvin
Figure 2007101999003_26
479 content be polyethyleneterephthalate master batch → B layer of 20wt%
3.99wt% has 0.1wt%SiO 2Silysia
Figure 2007101999003_27
340 (Fuji Silysia, SV value JP) is that 800 polyethyleneterephthalate and 1wt%SV value are 700 and Tinuvin
Figure 2007101999003_28
479 content are polyethyleneterephthalate master batch → C layer of 20wt%
By twin screw extruder, Tinuvin
Figure 2007101999003_29
479 is mixed in the commercial pet polymer.In polycondensation process, added SiO 2Particle.IPA in the polyester (=m-phthalic acid) content is that 0.1wt% and DEG (glycol ether) content are 1wt%.
It is interior also through the seam die that polymeric blends is fed into pin hole (pinole) (geat cover) together, and electrostatic precipitation is on the chill roll that is maintained under 60 ℃.Then under following condition, vertically, cross directional stretch film then:
Longitudinal stretching Heating temperature 75-115 ℃
Draft temperature 115 ℃
The longitudinal stretching ratio 3.7
Cross directional stretch Heating temperature 100 ℃
Draft temperature 110 ℃
The cross directional stretch ratio 4.0
Heat setting type Temperature 237-150 ℃
Time length 2 s
Under 200-150 ℃, relaxing on TD 7 ％
The total thickness of the film that so obtains is that the thickness of 20 microns and outer A is that 5 microns thickness with outer C are 2 microns.Transparency is 88%, and the last Young's modulus of MD is 4920N/mm 2And the Young's modulus on the TD is 5105N/mm 2The last F5 value of MD is 100N/mm 2And the F5 value on the TD is 102N/mm 2Under 200 ℃, be 2.7% and be 0.1% on TD in the shrinking percentage on the MD.
In case switch to this film type, do not observe the interior pressure change of forcing machine of the B of basic unit.Because the B layer is thicker and stable, the variation that therefore the A layer is little in forcing machine is to the not influence of operational stability of the producing apparatus of film.
Oder levels is 1.8.
Weather 1000 hours (through the light incident of layer A) afterwards tensile strength (UTS) be initial value 91% and be 67% of initial value after 3000 hours.
Embodiment 4
Be similar to Comparative Examples 1, but the compound (CGX UVA006) of use 0.5wt% formula (II) (Ciba SC, CH).
Oder levels is 1.8.
In case switch to this film type, do not observe the pressure change in the die head.Tensile strength values (UTS) is 70% of an initial value after 1000 hours Weathers.

Claims (18)

1. the single or multiple lift polyester film of diaxial orientation, it is at least a to it is characterized in that it comprises in the UV stabilizer of formula (I):
Figure FSB00000721927000011
Wherein:
R 1Be-H ,-the C1-C12 alkyl ,-aryl ,-S-(C1-C12) alkyl or-O-R 9Or-O-(C1-C5)-alkylidene group-C (O) O-R 9, wherein
R 9Be-aryl or-the C1-C12 alkyl,
R 3And R 4Be
Figure FSB00000721927000012
With
R 2, R 5, R 6, R 7And R 8Independently of one another expression-H ,-(C1-C12)-alkyl ,-O-(C1-C12)-alkyl ,-aryl or-the O-aryl,
When wherein said alkyl has greater than two carbon atoms and alkylidene group can be straight or branched when having greater than a carbon atom.
2. the polyester film of claim 1, it contains in the UV stabilizer of with good grounds formula (I) at least a, wherein:
R 1Expression-O-R 9Or-O-CH (CH 3)-C (O) O-R 9, wherein
R 9Represent hexyl, heptyl or octyl group and
R 2, R 5, R 6, R 7And R 8Expression-H.
3. the polyester film of claim 1, it contains in the UV stabilizer of with good grounds formula (I) at least a, wherein:
R 1Be-O-R 9, wherein
R 9Be octyl group and
R 2, R 5, R 6, R 7And R 8Expression-H.
4. the polyester film of claim 1, it contains in the UV stabilizer of with good grounds formula (I) at least a, wherein:
R 1Be-O-CH (CH 3)-C (O) O-R 9, wherein
R 9Represent octyl group with
R 2, R 5, R 6, R 7And R 8Expression-H.
5. any one polyester film of claim 1-4, wherein film is an individual layer.
6. any one polyester film of claim 1-4, wherein film is a multiwalled.
7. any one polyester film of claim 1-4, it contains in the UV stabilizer according to formula (I) that consumption is 0.1-10wt% at least a, with respect to the quality meter of the layer that contains UV stabilizer.
8. any one polyester film of claim 1-4, wherein film contains a kind of or more kinds of stablizer and/or anti.
9. any one polyester film of claim 1-4, wherein film contains free-radical scavengers.
10. any one polyester film of claim 1-4, wherein film contains fire retardant.
11. the polyester film of claim 6, wherein film has greater than two-layer and be included in one deck or the two outer layers greater than 25% UV stabilizer.
12. the polyester film of claim 6, wherein film has greater than two-layer and be included in one deck skin greater than 25% UV stabilizer.
13. the polyester film of claim 6 does not wherein have layer to contain the UV stabilizer greater than 7wt%, with respect to the quality meter of the layer that contains UV stabilizer.
14. any one polyester film of claim 1-4, wherein under 200 ℃ on vertical and horizontal, the shrinking percentage of film is less than 10%.
15. any one polyester film of claim 1-4, wherein in the rate of expansion of 100 ℃ of following films less than 3%.
16. any one polyester film of claim 1-4, wherein the Young's modulus on vertical and horizontal is greater than 3000N/mm 2
17. any one polyester film of claim 1-4, wherein the F5-value on the vertical and horizontal promptly the power under 5% elongation greater than 80N/mm 2
18. the method for the polyester film of preparation claim 1; Wherein at first in forcing machine, compress and plastify the polymkeric substance or the polymeric blends of said layer, be configured as flat plasticizing film through list or multilayer nozzle then, push said plasticizing film through the seam die; And by chill roll and one or more pull roll traction; Biaxial stretch-formed subsequently, heat setting type and coiling is characterized in that at least one tunic comprises the UV stabilizer according to formula (I).
CN2007101999003A 2006-12-19 2007-12-18 Single layer or multilayer, stabilised polyester film Active CN101205307B (en)

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DE102006059888A DE102006059888A1 (en) 2006-12-19 2006-12-19 Biaxially oriented mono or multilayered polyester film stabilized against ultraviolet light comprises substituted triazine compounds
DE200710001443 DE102007001443A1 (en) 2007-01-03 2007-01-03 Biaxially oriented mono or multilayered polyester film stabilized against ultraviolet light comprises substituted triazine compounds
DE102007001443.2 2007-01-03
DE102007045581A DE102007045581A1 (en) 2007-09-24 2007-09-24 Biaxially oriented mono or multilayered polyester film stabilized against ultraviolet light comprises substituted triazine compounds
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CN102317358B (en) * 2009-02-17 2015-02-18 帝斯曼知识产权资产管理有限公司 Sheet having high water vapor permeability
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CN1178527A (en) * 1995-03-15 1998-04-08 希巴特殊化学控股公司 Biphenyl-substituted triazines as light stabilizer
CN1334287A (en) * 2000-07-26 2002-02-06 西巴特殊化学品控股有限公司 Low-thickness transparent polymer articles
US6627695B2 (en) * 2000-02-28 2003-09-30 Mitsubishi Polyester Film Gmbh White, biaxially oriented and UV-resistant polyester film with cycloolefin copolymer (COC), its use and process for its production
US20040067379A1 (en) * 2000-02-19 2004-04-08 Herbert Peiffer Transparent, sealable, UV-resistant polyester film, its use and process for its production
US6811841B1 (en) * 2003-04-15 2004-11-02 3M Innovative Properties Company Light-stable structures

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Publication number Priority date Publication date Assignee Title
CN1178527A (en) * 1995-03-15 1998-04-08 希巴特殊化学控股公司 Biphenyl-substituted triazines as light stabilizer
US20040067379A1 (en) * 2000-02-19 2004-04-08 Herbert Peiffer Transparent, sealable, UV-resistant polyester film, its use and process for its production
US6627695B2 (en) * 2000-02-28 2003-09-30 Mitsubishi Polyester Film Gmbh White, biaxially oriented and UV-resistant polyester film with cycloolefin copolymer (COC), its use and process for its production
CN1334287A (en) * 2000-07-26 2002-02-06 西巴特殊化学品控股有限公司 Low-thickness transparent polymer articles
US6811841B1 (en) * 2003-04-15 2004-11-02 3M Innovative Properties Company Light-stable structures

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