BIAXIALLY ORIENTED POLYESTER FILMS, USE OF POLYESTER FILM, PHOTOVOLTAIC CELL, PROCESS FOR MANUFACTUR

专利摘要:
biaxially oriented polyester films, use of polyester film, photovoltaic cell, process for making a polyester film, method to improve resistance to hydrolysis and use of a metal cation the present invention relates to a film of biaxially oriented polyester, comprising polyester and at least one hydrolysis stabilizer selected from a glycidyl ester of a branched monocarboxylic acid, wherein the monocarboxylic acid contains from 5 to 50 carbon atoms, in which said stabilizer of hydrolysis is present in the film in the form of its reaction product with at least some of the end groups of said polyester, and in which said reaction product is obtained by reacting the hydrolysis stabilizer with the end groups of the polyols -ter, in the presence of a metallic cation selected from the group consisting of metal cations from group i and group ii.
公开号:BR112013022881B1
申请号:R112013022881-4
申请日:2012-03-07
公开日:2020-12-15
发明作者:William J. Brennan；Allan Lovatt；David R. Turner；Emma Ashford；Kirstin Jayne Forsyth；Simon Vernon Mortlock；William Bryden Goldie
申请人:Dupont Teijin Films U.S. Limited Partnership；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present invention relates to polyester films, in particular poly (ethylene terephthalate) (PET) films, which have an improved resistance to hydrolysis, and a process for their production. BACKGROUND OF THE INVENTION
[002] The advantageous mechanical properties, dimensional stability and optical properties of polyester films are well known. However, polyester films are susceptible to hydrolytic degradation, which results in a reduction of the intrinsic viscosity of the polymer, and further deterioration of one or more of the desirable properties, mentioned above, of the film, in particular the mechanical properties. Low resistance to hydrolysis is a particular problem when the film is used in conditions of high humidity and / or temperatures and / or in external applications, such as in photovoltaic cells (PV).
[003] The incorporation of hydrolysis stabilizers in the film is known to improve the hydrolysis resistance of polyester films. For example, the addition of carbodiimides as the final protective agents in polyester compositions has been proposed in US patents 5,885,709 and EP 0,838,500, among others, but these additives have a tendency to emit harmful gaseous by-products. US patent 2003 / 021,914-A1 describes that the use of polymeric carbodiimides as hydrolysis stabilizers reduces the tendency for gas to be released. US patent 2002 / 0.065.346-A1 describes hydrolysis stabilizers selected from a phenolic compound, an oxazoline and / or a monomeric or polymeric carbodiimide, optionally combined with an organic phosphite. GB 1,048,068 describes the use of copper salts of organic carboxylic acids as hydrolysis stabilizers. US patents 3,657,191 and US 3,869,427 describe the alteration of the terminal groups of the polyester through reaction with ethylene carbonate or monofunctional glycidyl ethers. Hydrolysis-resistant polyesters stabilized through the use of compounds containing the epoxy terminal group are also described in EP patent 0.292.251-A. EP 1,209,200 states that the combination of a glycidyl ester and a glycidyl ether in the presence of a catalyst that promotes the reaction between the glycidyl and carboxyl groups improves the hydrolysis resistance of the polyesters, although the description refers to polybutylene terephthalate (PBT), which crystallizes much faster than PET, and its use in the manufacture of injection molded materials. US patent 6,498,212 describes polyesters in which hydrolytic stability has been improved through the use of a polymeric terminal protective agent selected from ethyl epoxyethylene acrylate copolymers, epoxystyrene-butadiene-styrene block copolymers and amino copolymers polyethylene. The use of alkyl esters of epoxidated fatty acids (such as 2-ethylhexyl ester epoxidized stearic acid) and / or epoxidized fatty acid glycerides (such as soy or epoxidized flaxseed oil) as the stabilizers of hydrolysis in polyester compositions is described in patents CA 2,514,589-A, US 4,540,729, US 5,589,126, US 7,229,697, US 7,241,507, US 2005 / 0.137,299-1 A1, US 2007 / 0.238. 816-A1 and US 2007 / 0.237.972-A1. Other methods to improve the hydrolytic stability of poly (ethylene terephthalate) (PET) films include simultaneous control of parameters, such as intrinsic viscosity, diethylene glycol content and crystallinity, as described in EP patent 0.738,749 -THE. The control of intrinsic viscosity and crystallinity, in combination with the presence of an antioxidant, is described in EP patent 0.620.245-A, as enhanced characteristics of aging at elevated temperature (180 ° C), without impairing the delamination properties in the plane for polyester films used as insulating materials in motors and electric capacitors. US patents 4,115,350 and US 4,130,541 describe that the product of the reaction of polyesters with epoxidized alkyl esters of monocarboxylic acids, amides and thio-acids improves the thermal stability of polyester in the fibers and yarns produced from them. US patent 3,372,143 describes that the product of the reaction of polyesters with epoxidized alkoxy or aryloxy ethers, improves the dyeing capacity of the fibers produced from them.
[004] One of the problems associated with the incorporation of hydrolysis stabilizers in polyester films is that, although increasing the concentration of the additive improves the resistance to hydrolysis, it causes a reduction in the melting point and a deterioration of the mechanical properties of the polyester. One of the consequences of a reduction in mechanical properties is that the processability of the filmed polyester becomes poor, and the film's web breaks during manufacturing and further processing.
[005] Another problem with the use, in polyester films of the prior art, of hydrolysis stabilizers based on epoxidated fatty acids, particularly epoxidized fatty acid glycerides, is that these additives have a tendency to decompose during manufacture and processing of films, with the evolution of acrolein, a foul-smelling flammable and highly toxic substance.
[006] An additional problem with known hydrolysis stabilizers, particularly those based on certain multifunctional epoxidized fatty acid and glycidyl glyceride compounds, is the reduction in film quality and processability when such additives are incorporated into the film in an amount effective to provide improved hydrolysis resistance. In particular, these additives induce profile defects and unacceptable levels of the matrix lines in polyester films, that is, little uniformity in thickness and / or light transmission through the film web, and the extrudate may become impossible to process on one line of the film due to the break of the film frame. It is believed that these problems are at least partially attributable to crosslinking and gel formation, which interferes with the stretching process experienced by the film during its manufacture. An additional problem with the use of multifunctional glycidyl compounds as PET hydrolysis stabilizers is that their high rate of extension of the polyester chain increases the viscosity of the melt, which in turn reduces the extrusion output at a given temperature, and this is economically undesirable. Although viscosity could theoretically be reduced by increasing melting temperatures, this would lead to increased rates of polymer degradation and hydrolysis stabilizer and would cause gel formation. Gel formation is much less problematic in the manufacture of other polyester products, such as the injection of molded PBT products, partly due to the greater thickness of the products compared to the polyester film. BRIEF DESCRIPTION OF THE INVENTION
[007] It is an object of the present invention to provide alternative polyester films resistant to hydrolysis, in particular, in which the resistance to hydrolysis is improved, in particular, in which the film can be manufactured and used without the evolution of toxic by-products, in particular, maintaining or enhancing the ease and efficiency and economy of film making, without increasing the breakage of the film, in particular, where the level of the die line and profile defects are reduced and, in particular, without the detriment the mechanical and / or optical properties of the film. DETAILED DESCRIPTION OF THE INVENTION
[008] According to the present invention, a biaxially oriented polyester film is provided, comprising polyester (preferably poly (ethylene terephthalate)) and at least one hydrolysis stabilizer selected from an ester of a branched glycidyl monocarboxylic acid, in which the monocarboxylic acid contains 5 to 50 carbon atoms, in which said hydrolysis stabilizer is present in the film in the form of its reaction product with at least some of the said terminal groups polyester, and where the polyester film still comprises a metallic cation selected from the group consisting of Group I and Group II metal cations.
[009] In the present invention, said reaction product is obtained through the reaction of the hydrolysis stabilizer with the polyester terminal groups, in the presence of the Group I or Group II metal cations that catalyze the reaction.
[010] According to another aspect of the present invention, a biaxially oriented polyester film is provided which comprises polyester (preferably poly (ethylene terephthalate)) and at least one selected hydrolysis stabilizer from an ester of a branched glycidyl monocarboxylic acid, in which the monocarboxylic acid contains from 5 to 50 carbon atoms, in which said hydrolysis stabilizer is present in the film in the form of its reaction product with at least some of the end groups of said polyester, and in which said reaction product is obtained through the reaction of the hydrolysis stabilizer with the end groups of polyester, in the presence of a metallic cation selected from the group consisting of Group I metal cations and Group II.
[011] The hydrolysis stabilizer used in the present invention acts as a polyester end group protector through reaction with the carboxyl end groups and / or the hydroxyl end groups of the polyester, and the predominant reaction is believed to be with the groups carboxyl terminals. Carboxyl terminal groups have been shown to be primarily responsible for the hydrolytic degradation of polyesters, including poly (ethylene terephthalate). The glycidyl group of the hydrolysis stabilizer quickly reacts with the terminal groups of the polyester at elevated temperatures and, most importantly, reacts with zero elimination of toxic by-products during the manufacture of the modified polyester or during the subsequent manufacture and use of the polyester film. The hydrolysis stabilizer is also readily incorporated into the polyester.
[012] The metal cations are present in a catalytically active amount sufficient to catalyze the reaction between the hydrolysis stabilizer and at least some of the terminal groups of said polyester.
[013] In a preferred embodiment, the amount of the metal cation present in the film, and / or present in the reaction mixture during the hydrolysis reaction of the stabilizer with the polyester end groups, is at least 40 ppm, greater preferably at least 45 ppm, more preferably at least 65 ppm, most preferably at least 80 ppm and most preferably at least 100 ppm by weight, based on the amount of polyester produced. Preferably, the amount of the metal cation is not more than about 1,000 ppm, preferably not more than about 500 ppm, more preferably, not more than about 275 ppm, usually not more than about 200 ppm and, in an embodiment not exceeding about 150 ppm by weight, based on the amount of the polyester. Preferably, the amount of the metal cation is in the range from 45 ppm to 500 ppm, more preferably from 65 ppm to 275 ppm, most preferably from 100 ppm to 200 ppm by weight, relative to the amount of polyester.
[014] In an alternative embodiment, the amount of the metal cation present in the film, and / or present in the reaction mixture during the hydrolysis reaction of the stabilizer with the polyester end groups, is at least 10 ppm, preferably at least at least 15 ppm, more preferably at least 35 ppm, most preferably at least 50 ppm, and even more preferably at least 70 ppm by weight, relative to the amount of polyester produced. In the present embodiment, the amount of metallic cation is preferably not more than about 1,000 ppm, not more than about 500 ppm, more preferably not more than about 250 ppm, normally not more than about 150 ppm and , in an embodiment not exceeding about 100 ppm by weight, in relation to the amount of polyester. In the present embodiment, the amount of the metal cation, preferably in the range of 15 ppm to 500 ppm, more preferably from 35 ppm to 250 ppm, most preferably from 70 ppm to 150 ppm by weight, relative to the amount of polyester.
[015] As used herein, the terms "Group I" and "Group II" have their conventional chemical meaning and refer to the corresponding groups in the periodic table. In a preferred embodiment, the metal cations are Group I metal cations, preferably sodium or potassium, preferably sodium.
[016] It is believed that the catalytic effect is a result of the cation and, therefore, the corresponding anion of the catalyst can be any suitable negatively charged molecule or atom. In one embodiment, the anion is selected from hydroxide, polyacrylate, hydrogen carbonate, carboxylate, chlorine, acetate, formate and nitrate. In a preferred embodiment, the anion is selected from hydroxide or polyacrylate. Suitable polyacrylates are those that have a molecular weight of about 1,000 to about 10,000.
[017] Polyester film is a self-sufficient film or sheet which means a film or sheet capable of independent existence in the absence of a support base.
[018] The polyester of said polyester film is preferably poly (ethylene terephthalate) or polyethylene naphthalate, and most preferably, poly (ethylene terephthalate), but it can also contain relatively smaller amounts of one or more more residues derived from other dicarboxylic acids and / or diols. Other dicarboxylic acids include isophthalic acid, phthalic acid, 1,4-, 2,5-, 2,6- or 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, hexahydro-terephthalic acid, 1,10-decanedicarboxylic and aliphatic dicarboxylic acids of General Formula CnH2n (COOH) 2, where n is 2 to 8, such as succinic acid, sebacic acid, glutaric acid, adipic acid, azelaic acid, submeric acid or pyelic acid. Other diols include aliphatic and cycloaliphatic glycols, such as 1,4-cyclohexanedimethanol. Preferably, the polyester film contains only one dicarboxylic acid, i.e., terephthalic acid. Preferably, the polyester contains only one glycol, i.e., ethylene glycol. The polyester resin is the main component of the film, and comprises at least 50%, preferably at least 65%, more preferably, at least 80%, most preferably, at least 90%, and even more. preferably at least 95% by weight of the total weight of the film.
[019] The intrinsic viscosity of the polyester from which the film is manufactured is preferably at least about 0.65, more preferably at least about 0.70, most preferably at least about 0.75 and even more preferably, at least about 0.80.
[020] The formation of the polyester is conveniently carried out in a known manner through condensation or ester exchange, in general, at temperatures up to about 295 ° C. In a preferred embodiment, solid state polymerization can be used to increasing the intrinsic viscosity to the desired value, using conventional techniques well known in the art, for example, using a fluidized bed, such as a nitrogen fluidized bed or a vacuum fluidized bed using a rotary vacuum dryer.
[021] The hydrolysis stabilizer is preferably present in an amount in the range from about 0.1% to about 5%, more preferably, from about 0.1% to about 2 , 5%, even more preferably, from about 0.1% to about 2.0%, even more preferably, from about 0.3% to about 1.75%, still most preferably, from about 0.3% to about 1.5%, in relation to the total weight of the film.
[022] The branched monocarboxylic acid from which the hydrolysis stabilizer is derived contains from 5 to 50 carbon atoms, preferably from 5 to 25 carbon atoms, most preferably from 5 to 15 carbon atoms, even more preferably, from 8 to 12 carbon atoms, even more preferably, from 9 to 11 carbon atoms, and one embodiment contains 10 carbon atoms. The monocarboxylic acid is preferably saturated, that is, the carbon-carbon bonds in the molecule are single bonds. The branched monocarboxylic acid is preferably one in which the carbon atom adjacent to the carboxylic acid group (hereinafter referred to as the “α-carbon” atom) is a tertiary carbon atom, that is, it is linked by means of three simple carbon-carbon bonds to three carbon atoms with the exception of the carbon atom of the carboxylic acid group and each of said three carbon atoms can be part of an alkylene group or an alkyl group. Monocarboxylic acid is preferably a synthetic material, that is, it is manufactured by means of organic synthesis which comprises at least one synthesis step according to conventional processes (see, for example, publication WO-01 / 56966-A1), rather than a naturally occurring material (such as a fatty acid), which may need isolation from a naturally occurring substance.
[023] The hydrolysis stabilizer used in the present invention can be manufactured by the known reaction of epichlorohydrin with the desired branched monocarboxylic acid. The reaction can be carried out using conventional acid or basic catalysts, such as alkali metal carboxylates and quaternary ammonium halides, usually at elevated temperatures (temperatures in the range 50 to 120 ° C are typical).
[024] In one embodiment, a single hydrolysis stabilizer is used in the polyester film, but in a preferred embodiment, a mixture of hydrolysis stabilizers, as defined herein, may be used, in which case the total concentration of the stabilizers in hydrolysis is within the ranges mentioned above. The glycidyl ester (s) described herein is preferably / are used according to the present invention in the absence of other hydrolysis stabilizers (i.e., in the absence of a stabilizer) hydrolysis which is not an ester of a branched glycidyl monocarboxylic acid) and in an embodiment in the absence of the glycidyl ether compound (s), in particular, the di- or poly-glycidyl ether compounds for the reasons explained above. In one embodiment, the polyester film described herein essentially consists of poly (ethylene terephthalate) and at least one hydrolysis stabilizer selected from an ester of a branched glycidyl monocarboxylic acid. In one embodiment of the present invention, the hydrolysis stabilizer (s) used in the present invention essentially consist of at least one ester of a branched glycidyl monocarboxylic acid.
[025] In one embodiment, the hydrolysis stabilizer has Formula (I):
- wherein: - R1e R2 are independently selected from alkyl, and preferably at least one (and, in one embodiment only) of R1e R2 is selected from methyl; - R3is selected from hydrogen and alkyl, and preferably from alkyl, and - where the total number of carbon atoms in the alkyl groups R1, R2 and R3 is from 3 to 48, preferably from 3 to 23, most preferably, from 3 to 13, most preferably, from 6 to 10, still preferably, from 7 to 9, and in one embodiment it is 8.
[026] In one embodiment, a mixture of hydrolysis stabilizers is used, each independently selected, according to Formula (I), and in one embodiment so that the total number of carbon atoms in the alkyl groups R1, R2e R3in each component of the mixture is the same.
[027] In a preferred embodiment, R1is selected from methyl, and R2e R3is independently selected from alkyl, wherein the total number of carbon atoms in the alkyl groups of R2e R3is preferably from 2 to 47 from 2 to 22, most preferably, from 2 to 12, most preferably, from 5 to 9, even more preferably, from 6 to 8, and in one embodiment it is 7. In in one embodiment, a mixture of these preferred hydrolysis stabilizers is preferably used so that the total number of carbon atoms in the alkyl groups R1, R2 and R3 in each component of the mixture is the same.
[028] As used herein, the term "alkyl" most preferably refers to an unsubstituted straight chain acyclic hydrocarbon group of Formula [-CnH2n + 1].
[029] The hydrolysis stabilizer, for example, the compound of Formula (I) above, may have quality, in which case the hydrolysis stabilizer may be present as the enantiomer or as a mixture of enantiomers.
[030] In one embodiment, the hydrolysis stabilizer preferably has a viscosity of less than 100 mPa.s, more preferably, less than 50 mPa.s, more preferably, less than 25 mPa.s at 20 ° C , measured according to ASTM D445.
[031] The hydrolysis stabilizer used in the present invention reacts with polyester at elevated temperatures, usually between about 160 ° C and 300 ° C, and reacts with rapid reaction times, usually much less than 1 second at 290 ° C.
[032] The hydrolysis stabilizer can be introduced at various stages during the film production process, that is: (1) Adding the additive, during the manufacture of the polyester from its monomers, and this would normally be done at the end of the polymerization process, immediately before extrusion into pellets. In one embodiment, the modified polyester can then be further treated by solid state polymerization, to increase the IV to a desired value. (2) Reacting the additive with the separate (off-line) polyester chip by melting the chip, mixing the molten material with the additive, then re-extruding and pelleting the modified polyester into chips. (3) Adding the additive (usually, where the additive is a liquid) to the polymer sliver, before or during the introduction of the polymer into the extruder used in the filmmaking process (for example, by adding the additive to the polymer in the extruder dispenser) and then extruding this mixture, allowing the additive and polyester to react together in the extruder (usually a twin screw extruder). (4) Injecting the additive (usually, where the additive is a liquid), in the molten polymer resulting from the extrusion process (that is, since the polymer is in the molten state, inside the extruder, usually an extruder double screw, and usually after the polymer passes through any devolatilization zone), but before the polymer is cast into a film. (5) Adding the additive during the manufacture of the polyester from its monomers, which is preferably carried out at the end of the polymerization process, before direct extrusion, in a film. The direct extrusion process is referred to herein as "coupling polymerization film production" or "closed coupling polymerization film production", in which the intermediate pelletizing step is dispensed with, and is particularly advantageous. A closed coupling process can be operated with a static or dynamic mixing device between the polymerization reactor and the film matrix, in which the mixing is carried out after the addition of the hydrolysis stabilizer. Static and dynamic mixing systems are conventional in the state of the art. In a static mixing device, the device of the non-moving elements continuously mixes the materials while melt flows flow through the mixer. Suitable dynamic mixing systems include Archimedes extruders or other screw systems. In a preferred embodiment of the present invention, the closed coupling process is operated with a static mixing device, and the Depositors have surprisingly observed that sufficient mixing to achieve the benefits of the present invention can only be obtained with a static mixing device. It is surprising that a closed coupling process applied to this system is able to dispense with dynamic mixing without detriment to the properties of the final film. In the closed coupling process, a step of polymerization intervention in the solid state can be and is preferably avoided. The closed coupling process reduces the amount of water present in the polymer, thus avoiding the need for a drying step prior to the formation of the film, and also reducing the amount of water present in the polymer matrix available for the reaction with the stabilizer of hydrolysis. The reduced water content allows the solid state polymerization intervention step to be dispensed with, and allows the polyester film to tolerate a high content of the carboxyl terminal group without loss of hydrolytic stability. Therefore, in the present embodiment, the content of the carboxyl terminal group is preferably in the range from about 15x10-6 to about 50x10-6 milliequivalents / g (meq / g), more preferably, from about 20 x10-6a about 40x10-6meq / g, while a typical SSP process reduces the content of the carboxyl terminal group to less than about 15 x10-6meq / g, preferably about 10x x10-6meq / g . The carboxyl content is determined by titration with sodium hydroxide after dissolving the polymer in hot benzyl alcohol.
[033] In one embodiment, the hydrolysis stabilizer is introduced via one of the routes (2), (3) and (4) above, preferably via the route (4). In one embodiment, a concentrate is produced by adding an excess amount of the hydrolysis stabilizer, in relation to the desired amount in the final film, and this is of particular use for the path (2) of the above process. In a further preferred embodiment, the hydrolysis stabilizer is introduced via route (5).
[034] In the present invention, the metal cation (s) can be added to the polyester or its monomers before or simultaneously with the addition of the hydrolysis stabilizer. Alternatively, the metal cation (s) can be added to the hydrolysis stabilizer before or simultaneously with the addition of said hydrolysis stabilizer to the polyester or its monomers. Preferably, the metal cation (s) is (are) added to the polyester or its monomers and, preferably, prior to the addition of the hydrolysis stabilizer. In a preferred embodiment, metal cations are added at the beginning of the polymerization reaction to prepare the polyester.
[035] Depositors surprisingly observed the product's improved performance using the process path (4), and in particular, the films manufactured by this path demonstrate an improved hydrolytic stability, compared to the films manufactured using the concentrate technology with the via (2) above. It is believed that the relatively late addition of the hydrolysis stabilizer to the polyester in the extrusion process minimizes the increase in the carboxyl terminal groups caused by thermal degradation during the manufacture of the film. In addition, the advantage of the path (4) over the concentrate path, for example, is that it allows a greater use of the recovered film (that is, the waste film from the film-making process, for example, resulting of the “cutting edge” normally performed, after the elastifying stage, to provide a film of uniform width). The recovered polyester usually has a low intrinsic viscosity and a higher concentration of the carboxyl end groups than the virgin polyester chip and the relatively late addition of the hydrolysis stabilizer allows the stabilization of the virgin and recovered polyester. The ability to use high levels of recovery, providing improved hydrolysis stability is a particular advantage of the present invention.
[036] The surprisingly improved product performance was also observed using the process path (5), again in terms of improved hydrolytic stability.
[037] In one embodiment, the film can still comprise a UV absorber. The UV absorber has a much higher extinction coefficient than that of polyester in such a way that most of the incident UV light is absorbed by the UV absorber, instead of polyester. The UV absorber, in general, dissipates the absorbed energy as heat, therefore preventing the degradation of the polymer chain, and improving the stability of the polyester to UV light. Typically, the UV absorber is an organic UV absorber, and suitable examples include those described in Encyclopaedia of Chemical Technology, Kirk-Othmer, Third Edition, John Wiley & Sons, Volume 23, pages 615-627. Particular examples of UV absorbers include benzophenones, benzotriazoles (US patents 4,684,679, US 4,812,498 and US 4,681,905), benzoxazinones (US patents 4,446,262, US 5,251,064 and US 5,264,539), and triazines (US patents 3,244,708, US 3,843,371, US 4,619,956, US 5,288,778 and WO 94/05645). The UV absorber can be incorporated into the film according to one of the methods described herein. In one embodiment, the UV absorber can be chemically incorporated into the polyester chain. EP-A-0.006.686, EP-A-0.031.202, EP-A-0.031.203 and EP-A-0.076.582, for example, describe the incorporation of a benzophenone in the polyester. The specific description of said documents in relation to UV absorbers is hereby incorporated by reference. In a particularly preferred embodiment, the improved UV stability in the present invention is provided by the triazines, more preferably the hydroxyphenyltriazines and, most preferably, the hydroxyphenyltriazine compounds of Formula (II):
- where R is hydrogen, C1-C18 alkyl, C2-C6 alkyl substituted by halogen or C1-C12 alkoxy, or is benzyl, and R1 is hydrogen or methyl. Preferably R is C1-C12 alkyl or benzyl, more preferably C3-C6 alkyl, and in particular hexyl. R1 is preferably hydrogen. An especially preferred UV absorber is 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- (hexyl) oxy-phenol, which is commercially available as Tinuvin ™ 1577 FF from Ciba -Additives.
[038] The amount of UV absorber is preferably in the range from 0.1% to 10%, more preferably 0.2% to 7%, most preferably 0.6% at 4%, even more preferably, from 0.8% to 2%, and even more preferably, from 0.9% to 1.2%, by weight, in relation to the total weight of the film.
[039] Preferably, the film still comprises an antioxidant. A range of antioxidants can be used, such as antioxidants that operate by trapping radicals or by decomposing peroxide. Suitable radical capture antioxidants include hindered phenols, secondary aromatic amines and hindered amines, such as Tinuvin ™ 770 (Ciba-Geigy). Suitable peroxide decomposition antioxidants include trivalent phosphorus compounds, such as phosphonites, phosphites (eg, triphenyl phosphate and trialkyl phosphites) and thiosinergists (eg, thiodipropionic acid esters, such as thiodipropionic acid esters dilauryl). The prevented phenol antioxidants are preferred. A particularly preferred hindered phenol is tetrakis- (methylene 3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl-propionate) methane, which is commercially available as Irganox ™ 1010 (Ciba-Geigy) Others Suitable commercially available hindered phenols include Irganox ™ 1035, 1076, 1098 and 1330 (Ciba-Geigy), Santanox ™ R (Monsanto), Cyanox ™ antioxidants (American Cyanamid) and Goodrite ™ antioxidants (BF Goodrich). in the polyester film, it is preferably in the range from 50 ppm to 5,000 ppm of the polyester and, most preferably, in the range from 300 ppm to 1,500 ppm, in particular in the range from 400 ppm to 1,200 ppm , and especially in the range from 450 ppm to 600 ppm. A mixture of more than one antioxidant can be used, in which case the total concentration of it is preferably within the ranges mentioned above. can be done through techniques conventional and preferably by mixing with the monomeric reagents from which the polyester is derived, particularly at the end of the direct esterification or ester exchange reaction, before polycondensation.
[040] The film can still comprise any other additive conventionally used in the manufacture of polyester films. Therefore, agents such as crosslinking agents, dyes, fillers, pigments, disposal agents, lubricants, radical scavengers, thermal stabilizers, flame retardants and inhibitors, anti-blocking agents, active surface agents, slip aids, gloss enhancers, prodegradants, viscosity modifiers, and dispersion stabilizers can be incorporated as appropriate. Such components can be introduced into the polymer in a conventional manner. For example, by mixing with the monomeric reagents from which the film-forming polymer is derived, or the components can be mixed with the polymer by tumble or by dry combining or by composing an extruder, followed by cooling and usually grinding into granules or chips. Masterbatching technology can also be used.
[041] The film, in particular, can comprise a particulate charge that can improve handling and winding capacity during manufacture, and can be used to modulate optical properties. The particulate charge, for example, can be an inorganic particulate charge (for example, metal or metalloid oxides, such as alumina, titanium oxide, talc and silica (especially silica or precipitated silica or diatomaceous gels), calcined aluminum silicate and alkali metal salts, such as calcium and barium carbonates and sulphates). Any inorganic charge present must be finely divided, and the volume of the average particle diameter distributed (spherical diameter equivalent to 50% of the volume of all particles, read on the cumulative distribution curve in relation to the percentage (%) of the volume for the particle diameter - often referred to as the “D (v, 0.5)” value), is preferably in the range from 0.01 to 5 μm, most preferably 0.05 to 1.5 μm and, even more preferably, from 0.15 to 1.2 μm. Preferably, at least 90%, more preferably, at least 95% by volume of the particles of the inorganic fillers are within the volume range of the distributed average particle diameter of about 0.8 μm, and particularly of about 0.5 μm. The particle size of the charge particles can be measured by the electron microscope, Coulter counter, sedimentation analysis and static or dynamic light scattering. Preferably, the techniques are based on laser light diffraction. The average particle size can be determined by plotting a cumulative distribution curve that represents the percentage of the particle volume less than the selected particle sizes and by measuring the 50th percentile.
[042] The formation of the polyester film can be carried out using conventional extrusion techniques well known in the prior art. In general terms, the process comprises the steps of extruding a layer of molten polymer at a temperature within the range from about 280 to about 300 ° C, the sudden cooling of the extrudate and the orientation of the cooled extrudate. Orientation can be carried out by any process known in the art for producing a oriented film, for example, a tubular or flat film process. Biaxial orientation is achieved by pulling in two directions perpendicular to each other in the film plane to obtain a satisfactory combination of mechanical and physical properties. In a tubular process, simultaneous biaxial orientation can be accomplished by extruding a primary multilayer film tube which is subsequently cooled, reheated and then expanded by the internal pressure of the gas to induce the transversal orientation, and withdrawn at a rate that will induce longitudinal orientation. In the preferred flat film process, the film forming polyester is extruded through a slit in the die and quickly cooled over an icy molding drum to ensure that the polyester is abruptly cooled to the amorphous state. The orientation is then carried out by stretching the cooled extrudate in at least one direction, at a temperature above the glass transition temperature of the polyester. The sequential orientation can be carried out by traction of the flat cooled extrudate, first in one direction, usually in the longitudinal direction, that is, the frontal direction through the film stretching machine, and then in the transversal direction. The frontal stretching of the extrudate is conveniently carried out along a set of rotating rollers or between two pairs of rolling rolls, the transverse stretching then being carried out in an elastifying apparatus. The stretching, in general, is carried out in such a way that the dimension of the oriented film is 2 to 5, more preferably, 2.5 to 4.5 times its original dimension, in the direction or in each direction of stretching. Normally, the drawing is carried out at temperatures higher than the Tg of the polyester, preferably about 15 ° C higher than the Tg. Higher pull rates (for example, up to about 8 times) can be used if guidance in a single direction is required. It is not necessary to stretch equally on the machine and in the transverse directions although this is preferred if balanced properties are desired.
[043] The stretched film can be, and most preferably, stabilized in a dimensional way by thermosetting on a three-dimensional support, at a temperature above the glass transition temperature of the polyester, but below the melting temperature of the same, to induce crystallization polyester. During thermofixation, a small amount of dimensional relaxation can be performed in the transverse direction (TD), through a procedure known as "convergence" "toe-in". Convergence (toe-in) may involve dimensional shrinkage of the order of 2 to 4%, but similar dimensional relaxation in the process or in the machine direction (MD) is difficult to achieve since low line voltages are necessary and control and rewinding of the film becomes problematic. The temperature of the thermosetting and the actual time will vary, depending on the composition of the film and its desired final thermal shrinkage, but should not be selected in a way that substantially degrades the film's resistance properties, such as tear resistance. Within these restrictions, a thermosetting temperature of about 180 to 245 ° C, in general, is desirable. In one embodiment, the thermosetting temperature is within the range of about 200 to about 225 ° C, which provides unexpected improvements in hydrolytic stability. After thermosetting, the film is usually cooled quickly in order to induce the desired crystallinity of the polyester.
[044] In one embodiment, the film can still be further stabilized through the use of an online relaxation stage. Alternatively, the relaxation treatment can be performed separately (offline). In this additional step, the film is heated to a temperature below that of the thermosetting phase, and with a very low strain of MD and TD. The tension experienced by the film is a low tension and usually less than 5 kg / m, preferably less than 3.5 kg / m, more preferably, in the range from 1 to about 2.5 kg m, and usually in the range of 1.5 to 2 kg / m of film width. For a relaxation process, which controls the speed of the film, the reduction in the speed of the film (and therefore the relaxation of tension) is usually in the range of 0 to 2.5%, preferably 0.5 to 2.0%. There is no increase in the transversal dimension of the film during the heat stabilization step. The temperature to be used for the thermal stabilization step can vary depending on the desired combination of the properties of the final film, with a higher temperature that provides better residual shrinkage properties, that is, lower. A temperature of 135 to 250 ° C, in general, is desirable, preferably from 150 to 230 ° C, more preferably, from 170 to 200 ° C. The duration of the heating will depend on the temperature used, but is usually at interval of 10 to 40 seconds, preferably with a duration of 20 to 30 seconds. This thermal stabilization process can be carried out using a variety of methods, including flat and vertical and “separate” (“offline”) configurations, as a separate process step or “in line”, as a continuation of the process film making. The film processed in this way will exhibit a lower thermal shrinkage than that produced in the absence of such post-thermoset relaxation.
[045] The thickness of the polyester film is preferably in the range from about 5 to about 500 μm, and most preferably not more than about 250 μm, and usually between about 37 μm and 150 μm.
[046] In one embodiment, the film is opaque, and these films are for specific use like the back panel of a PV (photovoltaic) cell. An opaque film preferably has an Optical Transmission Density (TOD) of at least 0.4, preferably at least 0.5, more preferably at least 0.6, most preferably at least 0.7, even more preferably, at least 1.0, and even more preferably, at least 1.5, and in one embodiment, preferably at least 2.0, preferably at least 3.0 and, most preferably, at least 4.0. An opaque film can be pigmented, as needed, and in one embodiment of the present invention, the film of the present invention is white, gray or black. Any suitable opacifying agent and / or bleaching agent can be used, as is known in the art.
[047] In an additional embodiment, the film is white, which can be done by incorporating an effective amount of a bleaching agent. Suitable bleaching agents include an inorganic particulate filler, such as those mentioned above, an incompatible resin filler, or a mixture of two or more of these fillers. Preferably, the bleaching agent is an inorganic particulate filler, preferably titanium dioxide and / or barium sulfate, and in a preferred embodiment, the filler is barium sulfate only. The amount of inorganic filler incorporated in the film is usually in the range from 5% to 30% by weight, preferably from 10% to 25% by weight, based on the weight of the layer polyester. A white film preferably has a whiteness index, measured as described herein, in the range from about 80 to about 120 units. A white film usually has a TOD in the range from 0.4 to 1.75, preferably at least 0.5, most preferably at least 0.6, most preferably at least 0.7.
[048] In an alternative embodiment, the film is gray or black, usually showing an TOD of at least 2.0, preferably at least 3.0, most preferably at least 4.0, and this can be achieved by incorporating an effective amount of an opacifying agent, such as carbon black, or a metallic filler, such as aluminum powder, as is known in the art. Carbon black is a preferred opacifying agent. Typically, this film comprises, in the range from about 0.3% to about 10%, preferably from 0.5% to 7%, more preferably, 1% to 5%, and most preferably furthermore, from 2% to 4% of an opacifying agent by weight based on the weight of the polyester. The opacifying agent suitably has an average particle diameter in the range from 0.01 to 1.5 μm, preferably 0.02 to 0.05 μm. This opaque film can optionally also contain a bleaching agent.
[049] In a preferred embodiment, the polyester film is translucent or optically transparent. As defined herein, an optically transparent film has a percentage (%) of diffuse visible light (opacity) not exceeding 30%, preferably not exceeding 15%, most preferably, not exceeding 10%, most preferably still, not more than 6%, even more preferably, not more than 3.5% and even more preferably, not more than 1.5%, and / or a total light transmittance (TLT) for the light in the region visible (400 nm to 700 nm) of at least 80%, preferably at least 85%, more preferably, at least about 90%, and preferably, an optically transparent film meets these opacity and TLT criteria. A translucent film can have a TLT of at least 50%, preferably at least 60%, and most preferably, at least 70%. In the present embodiment, any charge is mainly on the film for the purpose of improving the handling of the film and is normally present only in small quantities, in general, not exceeding about 0.5% and preferably less than about 0 , 3% by weight of the polyester, and is usually selected from silica and talc, preferably from silica. Titanium dioxide can also be useful in the present embodiment, for example, to modulate the translucency of the film as needed, and is also normally present only in small amounts, preferably not more than about 1.0%, of most preferably not more than about 0.5% and most preferably not more than about 0.3% by weight of the polyester. In the present embodiment, the film's curling ability (i.e., the absence of blockage or adhesion when the film is rolled on a roll) is enhanced, without an unacceptable reduction in opacity or other optical properties.
[050] The intrinsic viscosity of the polyester film is preferably at least 0.65, preferably at least 0.7, and in one embodiment, in the range from about 0.65 to about 0 , 75. The use of polyester films, with a relatively high intrinsic viscosity, provides enhanced hydrolysis stability.
[051] In one embodiment, the polyester of the polyester film has a high temperature endothermic peak, at a temperature of (A) ° C and a low temperature endotherm peak at a temperature of (B) ° C, the two peaks to be measured by differential scanning calorimetry (DSC), where the value of (AB) is in the range from 15 ° C to 50 ° C, preferably in the range from 15 ° C to 45 ° C, most preferably, in the range from 15 ° C to 40 ° C, and in one embodiment, in the range from 20 ° C to 40 ° C, and this feature can be achieved, as described in the present, through control of the thermosetting temperature for the specific polyester to be used. The advantage of presenting values (A-B), within the ranges described in the present invention is to obtain a surprising improvement in hydrolytic stability.
[052] The polyester film preferably exhibits less shrinkage, preferably less than 3% at 150 ° C for 30 minutes, more preferably less than 2%, more preferably less than 1.5 %, and even more preferably, less than 1.0%, particularly on the machine (longitudinal dimension) of the film, in particular a biaxially oriented film and, preferably, these low shrinkage values are presented in the two dimensions of the film (ie , in longitudinal and transversal dimensions).
[053] In addition to an improved resistance to hydrolysis, the polyester films of the present invention present a surprising improvement in the quality and uniformity of the film, in relation to previous films of the prior art, particularly those containing hydrolysis stabilizers that comprise epoxidated fatty acid glycerides. In particular, the films of the present invention exhibit less defects in profile and / or matrix lines, improved uniformity of thickness and light transmission through the film web; and improved processability, without defects or breaks in the film's plot.
[054] In one embodiment, the film described above may have one or more additional layers arranged on one or both of its surfaces, to form a composite structure, for example, to provide additional mechanical strength or electrical insulation. The formation of this composite structure can be carried out through coextrusion, or through the simultaneous coextrusion of the respective layers of film formation through independent holes of a matrix of multi-holes, and then joining the stationary fused layers or, preferably, through a single channel coextrusion in which melt flows of the respective polymers are first joined within a channel leading to a matrix conductor, and then extruded together from the matrix orifice under aerodynamic flow conditions without intermixing to produce a multilayer film, which can be oriented and term adjusted as described in the present. Other methods of forming a multilayer film include laminating two or more preformed layers, and coating a film-forming layer on one or both surfaces of a base layer. The coating can be carried out using any suitable coating technique, including engraving roller coating, reverse roller coating, dip coating, ball coating, extrusion coating, melt coating or electrostatic spray coating. Any coating step, preferably, avoids the use of the organic solvent and, most preferably, is carried out “in line”, that is, in which the coating step occurs during the manufacture of films and before, during, or between any stretch operation employed.
[055] Any additional layer, preferably, is selected from the polyesters derived from the dicarboxylic acids and diols described above, and preferably from PET or PET-based polyesters. Any additional layer may comprise any of the aforementioned additives, in particular one or more additives independently selected from the hydrolysis stabilizer (s), UV absorber (s), antioxidant (s) and inorganic filler (s) particulate (s), wherein the additive (s) in any additional layer may be the same or different from any additive in the film of the present invention described above, and in which said additive (s) and, in particular, the hydrolysis stabilizer (s) may be the same or different from those described above. The additional layer has a thickness, preferably in the range from about 50 to about 500 μm, more preferably, not more than about 250 μm, and usually between about 100 μm and 250 μm, most preferably still, between about 100 μm and 150 μm.
[056] In one embodiment of the present invention, the film described above has an additional polymer layer arranged on a first surface of the same, preferably without any other layer on the second surface of said film. In the present embodiment, the film of the present invention is preferably an opaque or white film, and the additional polymer layer is preferably transparent, with an opacity of not more than about 30%, normally not more than about 20% and, in one embodiment, not more than about 15%. The film, in accordance with the present embodiment of the present invention is of particular use as a back plane of a PV (photovoltaic) cell.
[057] The film of the present invention is intended and is adapted for use in any environment where hydrolytic stability is critical, for example, in conditions of high humidity and temperatures, and in outdoor applications, and of particular interest in present, are the photovoltaic (PV) cells. The PV cell is a multilayer assembly that normally comprises a frontal plane, electrode layers, an active photovoltaic layer, and a posterior plane. Dye-sensitized PV cells are of particular interest, in which the active light-absorbing layer comprises a dye that is excited by absorbing incident light. The film of the present invention is of particular use as such, or as a layer present in the front or back plane of the photovoltaic cell, in particular the back plane.
[058] In accordance with an additional aspect of the present invention, a photovoltaic cell is provided which comprises the frontal plane, the electrode layers, an active photovoltaic layer, and a posterior plane, in which the frontal plane and / or the posterior plane comprises a film of the present invention, and particularly in which at least the rear plane comprises a film of the present invention.
[059] In accordance with an additional aspect of the present invention, a photovoltaic cell is provided which comprises the frontal plane (which may be a flexible polymeric frontal plane or a frontal glass plane), the electrode layers, an active photovoltaic layer, and a posterior plane, usually where the electrode layers and an active photovoltaic layer are encapsulated in a suitable encapsulant (such as an ethylene vinyl acetate (EVA) resin matrix), as is known in the prior art, and in that the back plane comprises a film of the present invention, preferably, in which said film is an opaque or white film, preferably, in which said film has an additional polymer layer arranged on a first surface thereof, preferably without any another additional layer on the second surface of said film, wherein the additional polymer layer is preferably transparent having an opacity of not more than about 30%, normally te, not more than about 20% and, in one embodiment, not more than about 15%. In such a PV cell, the film of the present invention is on the outermost part of the multilayer assembly and is normally exposed to the atmosphere, and said additional polymeric layer is laminated to the active photovoltaic layer, for example, using a suitable adhesive, such as EVE.
[060] In accordance with a further aspect of the present invention, a process is provided for the manufacture of a biaxially oriented polyester film, comprising polyester (preferably poly (ethylene terephthalate)), as defined herein, wherein the process comprises: (i) extruding a layer of molten polyester (preferably poly (ethylene terephthalate)) and a hydrolysis stabilizer selected from an ester of a glycidyl branched monocarboxylic acid, preferably , where the extrusion temperature is in the range from about 280 to about 300 ° C (more preferably, in the range from about 285 to about 290 ° C), where the monocarboxylic acid contains 5 to 50 carbon atoms, in which the hydrolysis stabilizer is present in the extrudate in the form of its reaction product with at least some of the end groups of said polyester, and in which the polyester film still comprises a selected metallic cation linked from the group consisting of Group I and Group II metal cations and / or in which said reaction product is obtained by the reaction of the hydrolysis stabilizer with the polyester terminal groups, in the presence of a selected metal cation a from the group consisting of Group I and Group II metal cations; (ii) the sudden cooling of the extrudate; (iii) stretching the cooled extrudate in two mutually perpendicular directions; and (iv) thermofixing the film, preferably at a temperature in the range from stabilized by setting the temperature within the range from about 200 to about 225 ° C.
[061] In accordance with an additional aspect of the present invention, a method is provided to improve the hydrolysis resistance of a biaxially oriented polyester film, said method comprising the step of reacting a polyester (preferably poly (terephthalate) ethylene)) with at least one hydrolysis stabilizer selected from an ester of a branched glycidyl monocarboxylic acid, wherein the monocarboxylic acid contains from 5 to 50 carbon atoms, in which said hydrolysis stabilizer is present in the film in the form of its reaction product with at least some of the end groups of said polyester, and in which said reaction product is obtained by reacting the hydrolysis stabilizer with the end groups of the polyester, in the presence of a selected metallic cation from the group consisting of Group I and Group II metal cations. Said method further comprises the step of making said biaxially oriented polyester film, as described in the present, in particular, it comprises the steps of extrusion, rough cooling, stretching and the thermosetting steps of (i) to (iv) referred to above.
[062] In accordance with an additional aspect of the present invention, the use of a metal cation selected from the group consisting of Group I and Group II metal cations is provided, in particular, in which said use is the use of said metal cation as a catalyst, for the purpose of improving the hydrolysis resistance of a biaxially oriented polyester film (preferably poly (ethylene terephthalate)), which comprises at least one hydrolysis stabilizer selected from an ester of a branched glycidyl monocarboxylic acid, in which the monocarboxylic acid contains from 5 to 50 carbon atoms, in which said hydrolysis stabilizer is present in the film in the form of its reaction product with at least some of the terminal groups of said polyester, and in which said reaction product is obtained by the reaction of the hydrolysis stabilizer with the terminal groups of the polyester, in the presence of the metal cations of Group I or the Group II.
[063] In accordance with an additional aspect of the present invention, the use of a metal cation selected from the group consisting of Group I and Group II metal cations is provided, in particular, in which said use is the use of said metal cation as a catalyst, in combination with the use of a hydrolysis stabilizer selected from an ester of a branched glycidyl monocarboxylic acid, with the purpose of improving the hydrolysis resistance of a biaxially oriented polyester film (preferably , poly (ethylene terephthalate)), in which the monocarboxylic acid contains from 5 to 50 carbon atoms, in which said hydrolysis stabilizer is present in the film in the form of its reaction product with at least some of the terminal groups of said polyester, and in which said reaction product is obtained by the reaction of the hydrolysis stabilizer with the terminal groups of the polyester, in the presence of Group I metal cations or Group II.
[064] In accordance with an additional aspect of the present invention, the use of a film or a composite structure as defined herein is provided as a back plane in a photovoltaic cell. PROPERTY MEASUREMENT
[065] The following analyzes were used to characterize the films described in the present invention: (i) the clarity was evaluated by measuring the total light transmittance (TLT), and opacity (percentage (%) of the diffused visible light transmitted) through of the total thickness of the film using a spherical opacity meter M57D (Diffusion Systems) according to the standard test method ASTM D1003. (ii) Transmission Optical Density (TOD) was measured using a Macbeth TR 927 Densitometer (obtained from Dent and Woods Ltd, Basingstoke, UK) in the transmission mode. (iii) the whiteness index was measured using a Colorgard 2000 System, Model / 45 (manufactured by Pacific Scientific) and according to the principles of the ASTM D313 standard. (iv) the intrinsic viscosity (in dL / g units) was measured using solution viscosimetry, according to the ASTM D5225-98 (2003) standard on a Viscotek ™ Y-501C Relative Viscometer (see, for example, Hitchcock , Hammons & Yau at American Laboratory (August 1994) “The dual-capillary method for modern-day viscometry”) using a 0.5% solution by weight of the polyester solution in o-chlorophenol at 25 ° C and using Billmeyer single point method to calculate intrinsic viscosity:
- where: - n = the intrinsic viscosity (in dL / g), - nrel = the relative viscosity, - c = the concentration (in g / dL), and - nred = the reduced viscosity (in dL / g), which is equivalent to (nrel- 1) / c (also expressed as nsp / c where nsp is the specific viscosity). (v) the film's hydrolysis resistance was assessed through accelerated aging in an autoclave test. The film samples are cut into strips 10 mm wide and placed in an autoclave operating at 121 ° C and a pressure of 0.12 MPa (1.2 bar). The aging properties of the polymer were then measured at various time intervals. In particular, the tensile strength (brittleness) of the polyester was measured as the elongation at break (ETB) of the polymer. An ETB value greater than 100% is usually presented by a film that has not been aged. In general, a film remains useful in its final use, until the time when its ETB is reduced to less than 10%. The preferred films of the present invention have an ETB of at least 10% after at least 56 hours, preferably at least 60 hours, more preferably at least 64 hours, most preferably at least 68 hours , even more preferably, at least 72 hours, even more preferably, at least 76 hours, even more preferably, at least 84 hours, even more preferably, at least 88 hours, and even more preferably, at least 92 hours at 121 ° C and pressure of 0.12 MPa (1.2 bar) .pressure in the accelerated aging test described herein. (vi) elongation at break is measured according to the ASTM D882 test method. Using a straight edge and a calibrated sample cutter (10 mm and about 0.5 mm), five strips (100 mm in length) of the film are cut along the direction of the machine. Each sample is tested using an Instron Model 3111 material testing machine, using a pneumatically operated gripper equipped with acrylic contact faces. The temperature (23 ° C) and relative humidity (50%) are controlled. The crosshead speed (separation rate) is 25 mm.min-1. The deformation rate is 50%. It is calculated by dividing the separation rate by the initial distance between the claws (sample length). The equipment records the elongation at break of each sample The elongation at break (GB (%)) is defined as: - GB (%) = (elongation at break / Lo) x 100 - where L0 is the original length of the sample between the claws. (vii) the polyester film was tested for weathering according to ISO 4892-2. (viii) the thermal shrinkage was evaluated in the samples of films with dimensions of 200 mm x 10 mm, which were cut in specific directions in relation to the machine and transversal directions of the film and marked for visual measurement. The longest dimension of the sample (that is, the 200 mm dimension) corresponds to the direction of the film for which the shrinkage is being tested, that is, for the evaluation of the shrinkage in the machine direction, the sample dimension 200 mm is oriented along the direction of the film machine. After heating the sample to a predetermined temperature of 150 ° C (by placing it in an oven heated to that temperature) and keeping it for an interval of 30 minutes, it was cooled to room temperature and its dimensions manually measured manually. Thermal shrinkage was calculated and expressed as a percentage of the original length. (ix) differential scanning calorimetry (DSC) scans were obtained using a Perkin Elmer DSC 7 instrument. Samples of polyester film weighing 5 mg were encapsulated in a standard Perkin Elmer aluminum DSC crucible. The film and crucible were flattened to ensure that the film was partially restricted, to minimize the effects of orientation relaxation during heating. The sample was placed in the instrument's sample holder and heated to 80 ° C per minute from 30 to 300 ° C to record the relevant trace. A dry inert gas (nitrogen) purge was used. The temperature and axis of the thermal flow of the DSC instrument were fully calibrated for the experimental conditions, that is, for the heating rate and the gas flow rate. The values for peak temperatures, that is, the high temperature endothermic peak (A) and the low temperature endothermic peak (B) were taken as the maximum displacement above a baseline drawn since the beginning of each process. endothermic fusion until the end of each endothermic fusion process. Peak temperature measurements were derived using standard analysis procedures within the Perkin Elmer software. The precision and accuracy of the measurements were about 2 ° C. A sample scale is shown in Figure 1.
[066] The present invention is illustrated with reference to Figure 1, a typical DSC scan (thermal flow versus temperature) obtained by a polyester film, according to the present invention. The marked peak (A) in Figure 1 is the high temperature endothermic peak with a value of 250 ° C, and the marked peak (B) is the low temperature endothermic peak that has a value of 220 ° C and therefore the (AB) value is (250 to 220) = 30 ° C.
[067] The present invention is further illustrated by the following examples. The examples are not intended to limit the present invention, as described above. The change of details can be carried out without departing from the scope of the present invention. EXAMPLES CONTROL 1 COMPARATIVE EXAMPLES 1 AND 2 EXAMPLES 1 TO 12
[068] A first series of polyester films was prepared by measuring Cardura ™ E10P (Hexion Specialty Chemicals, Ohio, US; density 0.97 g / cm3), as the hydrolysis stabilizer directly to a melt stream of PET in a film screw twin-screw extruder, that is, as long as the polyester is in the molten state, at predetermined flow rates (0.800 or 960 mL / hr), as shown in Table 1 below, to provide the final film with the hydrolysis stabilizer in varying amounts. The flow rate of the PET was 93.3 kg / hr. The PET contained in Dispex G40 (Ciba / BASF; sodium salt of an acrylic copolymer, supplied as an aqueous dispersion at 40% solids), in quantities of 0, 250, 500 or 1,000 ppm (by weight in relation to the final weight of the polymer produced), which was added at the beginning of the polymerization process, together with terephthalic acid and ethylene glycol. The PET polymer still contained TiO2 in an amount of 0.3% by weight of the polyester, as well as SiO2 in an amount of 0.3% by weight of the polyester. The PET polymer chip had an intrinsic viscosity of 0.79.
[069] The mixture was subjected to melt extrusion at 285 ° C, molded on a cooled rotating drum and stretched in the direction of extrusion to about 2.9 times its original dimensions, at a temperature of 86 ° C. The film then cooled, it was passed to an elastifying oven, at a temperature of 110 ° C in which the film was dried and stretched in the lateral direction to about 3.4 times its original dimensions. The biaxially drawn film was thermo adjusted at a temperature of 220 ° C or 232 ° C. The final thickness of the resulting film was 50 μm. The film was translucent and had a TLT of 76%, and an opacity of 66%. The hydrolysis resistance of the film was evaluated by measuring its elongation at break, before and after accelerated aging, as defined in the present. The amount of hydrolysis stabilizer in the final film can be measured by 1H NMR (D2-1,1,2,2-tetrachloroethane, as a solvent; GSX-400 Delta instrument at 80 ° C).
[070] The results in Table 1 demonstrate that the hydrolysis stabilizer improves the hydrolysis resistance of the polyester film, even in the absence of the sodium ions provided by the Dispex additive (as is evident when Comparative Examples 1 and 2 are compared with Control 1), but that an even greater improvement in resistance to hydrolysis is observed after the addition of the sodium ions provided by the additive Dispex (as is evident, for example, when Examples 1 to 3 are compared with Comparative Example 1).
[071] In all the Examples, according to the present invention, described above, the uniformity of the film and the quality of the film were excellent, with a very low level of matrix lines or profile defects, there was no odor detected in the entire matrix of the film, and all films showed good processability. COMPARATIVE EXAMPLES 3 AND 4 EXAMPLES 13 TO 20
[072] A second series of polyester films was prepared using the procedure described above, except that the PET polymer contained 500 ppm of Irganox ™ 1010 (Ciba-Geigy) added at the beginning of the polymerization process, but did not contain TiO2 or SiO2, and the films were optically clear. The PET contained Dispex G40 in an amount of 500 ppm (by weight in relation to the final weight of the polymer produced) added at the beginning of the polymerization process. The hydrolysis resistance of the film was measured as before, and the results are shown in Table 2. The data demonstrates that the surprising effect of the combination of the hydrolysis stabilizer and the metal cation is also shown for the films of the present invention that are free from charge. The films in this second series, in general, show resistance to hydrolysis, which is superior to that of the films in the first series, and Depositors attribute this difference to the absence of charge in the second series, since the particles of the charge can act as a nucleating agent for further crystallization which leads to further embrittlement. COMPARATIVE EXAMPLE 5 EXAMPLE 21
[073] In these examples, polymerization and filmmaking processes were linked by means of a static mixing device in a closed coupling device, as described previously. The PET polymer was prepared by transesterification of dimethyl (DMT) and ethylene glycol and vacuum polymerized, according to conventional techniques. The Dispex additive was injected into the monomer stream before the polymerization stage, and in an amount of 500 ppm. The additive Cardura was injected into the polymer stream, after the polymerization reactor, and in an amount sufficient to provide 0.5% by weight in the final polymer. The film was manufactured differently, in general, according to the procedure described above, except that the final film had a thickness of 125 μm and the temperature of the crystallizer was 228 ° C. The results are shown in Table 3. TABLE1

TABLE 2
TABLE 3

n / m = not measured

权利要求:
Claims (31)
[0001]
1. BIAXIALLY ORIENTED POLYESTER FILM, characterized by comprising polyester and at least one hydrolysis stabilizer selected from an ester of a branched glycidyl monocarboxylic acid, in which the monocarboxylic acid has 5 to 50 carbon atoms, in which said hydrolysis stabilizer is present in the film in the form of its reaction product with at least some of the end groups of said polyester, and in which said reaction product is obtained by reacting the hydrolysis stabilizer with the end groups of polyester, in the presence of a metallic cation selected from the group consisting of metal cations from Group I and Group II.
[0002]
2. BIAXIALLY ORIENTED POLYESTER FILM, characterized by comprising polyester and, at least one hydrolysis stabilizer selected from an ester of a branched glycidyl monocarboxylic acid, in which the monocarboxylic acid has from 5 to 50 carbon atoms, in that said hydrolysis stabilizer is present in the film in the form of its reaction product, with at least some of the terminal groups of said polyester, and that the polyester film still comprises a metal cation selected from the group consisting of metal cations Group I.
[0003]
3. POLYESTER FILM, according to claim 1, characterized by the metal cations being selected from the group consisting of Group I metal cations.
[0004]
4. POLYESTER FILM according to any one of claims 1 to 3, characterized in that the metal cations are sodium cations.
[0005]
5. POLYESTER FILM according to any one of claims 1 to 4, characterized by the amount of the metal cation present in the film, and / or present in the reaction mixture during the reaction of the hydrolysis stabilizer with the end groups of the polyester being at least 45 ppm, preferably at least 65 ppm by weight, and / or more preferably not more than 500 ppm by weight, even more preferably not more than 200 ppm by weight, relative to the amount of polyester.
[0006]
POLYESTER FILM according to any one of claims 1 to 5, characterized in that the intrinsic viscosity of the polyester in the polyester film is at least 0.65 dL / g, preferably at least 0.7 dL / g, more preferably at least 0.75 dL / g, even more preferably at least 0.8 dL / g, where the intrinsic viscosity is measured by solution viscometry according to ASTM D5225-98 (2003) using a 0 solution , 5% by weight of polyester in o-chlorophenol at 25 ° C.
[0007]
7. POLYESTER FILM according to any one of claims 1 to 6, characterized in that the hydrolysis stabilizer is present in an amount in the range of 0.1% to 2.0%, in relation to the total weight of the layer.
[0008]
POLYESTER FILM according to any one of claims 1 to 7, characterized in that the hydrolysis stabilizer (s) in the polyester film consist (in) essentially of at least one ester of a branched glycidyl monocarboxylic acid.
[0009]
POLYESTER FILM according to any one of claims 1 to 8, characterized in that said branched monocarboxylic acid has from 5 to 15 carbon atoms, and / or in which said branched monocarboxylic acid is saturated, and / or said monocarboxylic acid branched is a synthetic material.
[0010]
POLYESTER FILM according to any one of claims 1 to 9, characterized in that said hydrolysis stabilizer is manufactured by reacting the epichlorohydrin with said branched monocarboxylic acid.
[0011]
11. POLYESTER FILM according to any one of claims 1 to 10, characterized in that said hydrolysis stabilizer has Formula (I):
[0012]
POLYESTER FILM according to any one of claims 1 to 11, characterized in that said hydrolysis stabilizer is reacted with the polyester by injecting the additive into the molten polymer before the polymer is molded into a film.
[0013]
13. POLYESTER FILM according to any one of claims 1 to 12, characterized in that the polyester film further comprises a UV absorber, and / or wherein the UV absorber is preferably an organic UV absorber, and more preferably selected from benzophenones, benzotriazoles, benzoxazinones and triazines, preferably from triazines, and preferably where the amount of UV absorber is in the range from 0.1% to 10% by weight, based on the total weight of the layer.
[0014]
POLYESTER FILM according to any one of claims 1 to 13, characterized in that it has been stabilized by setting the temperature within the range of 200 to 225 ° C, and / or in which the polyester of the polyester film has a high temperature endothermic peak at (A) ° C and low temperature endothermic peak at (B) ° C, both peaks are measured by differential scanning calorimetry (DSC), where the value (AB) is in the range of 15 ° C and 50 ° C.
[0015]
POLYESTER FILM according to any one of claims 1 to 14, characterized in that it exhibits an elongation at break, measured according to ASTM D882, of at least 10% after at least 56 hours, preferably at least 60 hours, more preferably at least 64 hours, even more preferably at least 68 hours, even more preferably at least 84 hours and, even more preferably at least 92 hours, when aged at 121 ° C and pressure of 0.12 MPa (1.2 bar) .
[0016]
16. POLYESTER FILM according to any one of claims 1 to 15, characterized in that it has an opacity of not more than 30% and / or a total light transmittance (TLT) of at least 50%, and / or in which the polyester film is selected from the group consisting of a white film, a black film and an opaque film.
[0017]
17. POLYESTER FILM according to any one of claims 1 to 16, characterized in that it further comprises an antioxidant.
[0018]
18. POLYESTER FILM according to any one of claims 1 to 17, characterized in that it has, on a first surface thereof, an additional polymeric layer, wherein said additional polymeric layer is a polyester layer that optionally comprises one or more more additives independently selected from hydrolysis stabilizer (s), UV absorber (s), antioxidant (s) and particulate inorganic filler (s), and / or in which the second layer has an opacity not more than 30%, where the polyester of the polyester layer is poly (ethylene terephthalate) or polyethylene naphthalate and may contain relatively small amounts of one or more residues derived from other dicarboxylic acids and / or diols.
[0019]
19. POLYESTER FILM according to any one of claims 1 to 18, characterized in that the polyester is poly (ethylene terephthalate).
[0020]
20. POLYESTER FILM according to any one of claims 1 to 17, characterized in that it has one or more additional layer (s) arranged on one or both surfaces of it to form a composite structure.
[0021]
21. POLYESTER FILM according to claim 20, characterized in that one or more additional layer (s) is (are) selected from poly (ethylene terephthalate) (PET) or polyesters based on PET, and comprise hydrolysis stabilizer (s) selected from the ester of a branched glycidyl monocarboxylic acid, in which the monocarboxylic acid has from 5 to 50 carbon atoms, in which said hydrolysis stabilizer is present in a or more additional layer (s) in the form of its reaction product with at least some of the polyester end groups, and preferably where the hydrolysis stabilizer in one or more additional layer (s), is in accordance defined in any one of claims 8 to 10.
[0022]
22. POLYESTER FILM, according to any one of claims 18 or 20 to 21, characterized in that the film is formed by co-extruding the respective film-forming layers.
[0023]
23. USE OF THE POLYESTER FILM, as defined in any one of claims 1 to 22, characterized in that it is like a layer in a photovoltaic cell, said photovoltaic cell comprising a frontal plane, electrode layer (s), an active photovoltaic layer and a rear plane, in particular, wherein said rear plane comprises said polyester film.
[0024]
24. PHOTOVOLTAIC CELL, characterized by comprising a frontal plane, electrode layer (s), an active photovoltaic layer and a posterior plane, wherein the frontal plane and / or the posterior plane comprises a film, as defined in any one of claims 1 to 22.
[0025]
25. PHOTOVOLTAIC CELL according to claim 24, characterized in that said electrode layers and active photovoltaic layer are encapsulated in a suitable encapsulant, and in which the posterior plane comprises a film, as defined in any of claims 1 to 22, and particularly, in which said film is an opaque or white film, in which said film has an additional polymeric layer arranged on a first surface, in which said additional layer exhibits an opacity not exceeding 30%, and in which said film it is in the outer part in the multilayer assembly.
[0026]
26. PROCESS FOR THE MANUFACTURE OF A biaxially oriented POLYESTER FILM, as defined in claim 1, characterized by the process comprising: (i) extrusion of the molten polyester layer and at least one hydrolysis stabilizer selected from an ester of a glycidyl branched monocarboxylic acid, in which the monocarboxylic acid has 5 to 50 carbon atoms, in which said hydrolysis stabilizer is present in the extrudate in the form of its reaction product with at least some of the terminal groups of said polyester, and in that said reaction product is obtained by reacting the hydrolysis stabilizer with the polyester end groups, in the presence of a metallic cation selected from the group consisting of Group I and Group II metal cations; (ii) sudden cooling of the extrudate; (iii) stretching of the extruded product suddenly cooled in two mutually perpendicular directions; and (iv) configuration of the heating of the film; optionally wherein the process comprises the additional step of producing said hydrolysis stabilizer by the reaction of epichlorohydrin with said branched monocarboxylic acid, and wherein the hydrolysis stabilizer is reacted with the polyester by injecting the additive into the molten polymer before said extrusion layer.
[0027]
27. PROCESS, according to claim 26, characterized in that the heating configuration is at a temperature in the range from 200 ° C to 225 ° C.
[0028]
28. PROCESS according to claim 26, characterized in that said biaxially oriented polyester film is as defined in any one of claims 3 to 22.
[0029]
29. A process according to any one of claims 26 to 28, characterized in that the film has one or more additional layer (s) arranged on one or both surfaces of it to form a composite structure and in which the process comprises the co-extrusion of the respective film-forming layers.
[0030]
30. METHOD FOR IMPROVING THE HYDROLYSIS RESISTANCE of a biaxially oriented polyester film, characterized by the said method comprising the reaction step of said polyester with at least one hydrolysis stabilizer selected from an ester of a branched glycidyl monocarboxylic acid, in which the monocarboxylic acid has 5 to 50 carbon atoms, in which said hydrolysis stabilizer is present in the film in the form of its reaction product, with at least some of the terminal groups of said polyester, in which said reaction product is obtained by the reaction of the hydrolysis stabilizer with the terminal polyester groups in the presence of a metallic cation selected from the group consisting of Group I and Group II metal cations, in which said biaxially oriented polyester film is as defined in any of claims 1 to 22.
[0031]
31. USE OF A METALLIC CATION, selected from the group consisting of Group I and Group II metallic cations, characterized by improving the hydrolysis resistance of a biaxially oriented polyester film, which comprises at least one stabilizer of hydrolysis selected from an ester of a branched glycidyl monocarboxylic acid, in which the monocarboxylic acid has from 5 to 50 carbon atoms, in which said hydrolysis stabilizer is present in the film in the form of its reaction product, with at least some of the end groups of said polyester, and in which said reaction product is obtained by reacting the hydrolysis stabilizer with the end groups of the polyester, in the presence of the metal cations of Group I or Group II, in which the polyester film biaxially oriented is as defined in any one of claims 1 to 22.

类似技术:

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公开号 | 公开日 | 专利标题

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BR112013022881B1|2020-12-15|BIAXIALLY ORIENTED POLYESTER FILMS, USE OF POLYESTER FILM, PHOTOVOLTAIC CELL, PROCESS FOR MANUFACTURING A POLYESTER FILM, METHOD TO IMPROVE HYDROLYSIS RESISTANCE AND USE OF A METALLIC CATION

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-03-31| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-08-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-09-24| B09X| Decision of grant: republication|

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2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161449897P| true| 2011-03-07|2011-03-07|

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US61/449,897|2011-03-07|

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GB1103855.1A|GB2488787A|2011-03-07|2011-03-07|Stabilised polyester films|

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GB1103855.1|2011-03-07|

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PCT/GB2012/000224|WO2012120260A1|2011-03-07|2012-03-07|Hydrolysis resistant polyester films|

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