Thin films comprising ethylene copolymers or ethylene terpolymers, methods for producing same, and their use as solar cell encapsulants

Abstract

A tie layer film comprising a polymer composition is provided, the film having an ethylene content in an amount ranging from 40% to 99.9% by weight, and a melt index (I2) measured according to ASTM D1238 (190°C and 2.16 kg load) of 0.1 g / 10 min to 100 g / 10 min, the polymer being prepared from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate. Also provided are molded articles comprising the two substrates and the film, and methods for producing the molded articles.

Description

[Technical Field]

[0001] Polymers used as tie layers in multilayer structures (e.g., flexible food packaging, containers, bottles, blow-molded tanks, pipes, or other applications requiring properties such as gas barrier while maintaining mechanical properties and cost requirements) generally have the primary role of ensuring good adhesion between different outer and inner layers, e.g., polyethylene or polypropylene in the outer layer and poly(ethylene-co-vinyl alcohol) or polyamide in the inner layer. [Background technology]

[0002] Therefore, it may be a combination of materials that does not inherently result in good compatibility and adhesion, and therefore the use of a third polymer that can combine the characteristics of the inner and outer layers is a strategy to overcome this scenario. Two main strategies are used for the selection of tie layer materials: 1. Using copolymers or terpolymers using comonomers with different chemical characteristics that allow good interaction (e.g., van der Waals forces, hydrogen bonding, co-crystallization, etc.) with both polymers in the layer structure; 2. Using copolymers or terpolymers that contain a fraction that is chemically similar / compatible with one polymer (usually a non-polar polymer) and another fraction that contains functional groups that result in reactive adhesion with the other polymer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent Application Publication No. 2021 / 0102014 Summary of the Invention [Problem to be solved by the invention]

[0004] Poly(ethylene-co-vinyl acetate) (EVA), both unmodified and grafted with functional groups (primarily maleic anhydride and acrylic acid), is a common base for tie layer grades. The present invention claims the use of a terpolymer comprising ethylene, vinyl acetate, and vinyl neodecanoate (VeoVa™ 10) as the base for the tie layer polymer. [Means for solving the problem]

[0005] This Summary is provided to introduce a selection of concepts that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0006] In one aspect, embodiments disclosed herein relate to a tie layer film comprising a polymer composition, the film comprising a polymer prepared from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate, having an ethylene content in an amount ranging from 40% to 99.9% by weight and having a melt index (I2) of 0.1 g / 10 min to 100 g / 10 min as measured according to ASTM D1238 at 190° C. and 2.16 kg load.

[0007] In another aspect, embodiments disclosed herein relate to a method of making a tie layer film comprising a polymer composition, the method comprising cast film extrusion, blown film extrusion, calendering, extrusion blow molding, injection molding, injection stretch blow molding, pipe extrusion, or thermoforming the film, the tie layer film comprising a polymer prepared from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate, having an ethylene content in an amount ranging from 40% to 99.9% by weight and having a melt index (I2) of 0.1 g / 10 min to 100 g / 10 min as measured according to ASTM D1238 (190°C and 2.16 kg load).

[0008] In another aspect, embodiments disclosed herein relate to a molded article comprising a film comprising a polymer composition, the film comprising two substrates and a polymer prepared from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate, the polymer having an ethylene content in an amount ranging from 40% to 99.9% by weight and having a melt index (I2) of 0.1 g / 10 min to 100 g / 10 min as measured according to ASTM D1238 at 190° C. and 2.16 kg load.

[0009] In another aspect, embodiments disclosed herein relate to a method of producing a molded article, the method comprising: applying a film comprising a polymer composition, the film comprising a polymer prepared from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate, having an ethylene content in an amount ranging from 40% to 99.9% by weight and having a melt index (I2) of 0.1 g / 10 min to 100 g / 10 min, as measured according to ASTM D1238 (190°C and 2.16 kg load), to a substrate; and placing a second substrate on the film.

[0010] Other aspects and advantages of the claimed subject matter will become apparent from the following description and appended claims. DETAILED DESCRIPTION OF THE INVENTION

[0011]

[0003] Embodiments disclosed herein relate to thin films comprising a polymer composition comprising a polymer prepared from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate, with the ethylene content ranging from 40% to 99.9% by weight. In one or more embodiments, the polymer composition can be prepared from the reaction of ethylene and one or more branched vinyl ester monomers and / or vinyl acetate monomers to modify various properties of the copolymer formed and the thin film formed therefrom, such as density, melt index (I2), melting point, electrical resistivity, hardness, softening point, light transmittance, haze, water vapor transmission rate, mechanical strength, UV cutoff wavelength, gloss, crystallinity, and glass transition temperature, among others.

[0012] Advantageously, in accordance with the present disclosure, the inclusion of branched vinyl esters in place of or in conjunction with vinyl acetate can reduce water vapor transmission rates (WVTR) while increasing low temperature flexibility.

[0013] polymer composition Copolymers and terpolymers The copolymers and terpolymers of the present disclosure can be made from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate, and have an ethylene content in an amount ranging from 40% to 99.9% by weight.

[0014] Branched Vinyl Ester Monomer In one or more embodiments, the branched vinyl ester may include a branched vinyl ester derived from an isomeric mixture of branched alkyl acids. The branched vinyl ester according to the present disclosure has the general chemical formula (I):

[0015] [ka]

[0016] (In the formula, R 1 , R 2 , and R 3may have a total carbon number ranging from C3 to C20. 1 , R 2 , and R 3 may all be alkyl chains with varying degrees of branching in some embodiments, or R 1 , R 2 , and R 3 A subset of may, in some embodiments, be independently selected from the group consisting of hydrogen, alkyl, or aryl.

[0017] In one or more embodiments, the vinyl carbonyl monomer has the general formula (II):

[0018] [ka]

[0019] (In the formula, R 4 and R 5 having a total of 6 or 7 carbon atoms), and the polymer composition has a number average molecular weight (M) in the range of 5 kDa to 10,000 kDa as determined by GPC. n In one or more embodiments, R 4 and R 5 may have a total carbon number of less than 6 or more than 7, and the polymer composition may have a M of up to 10,000 kDa. n That is, M n If R is less than 5 kDa, 4 and R 5 may have a total carbon number of less than 6 or more than 7, but M n When R is higher than 5 kDa, for example, in the range of 5 kDa to 10,000 kDa, 4 and R 5 may contain a total of 6 or 7 carbon atoms. In certain embodiments, R 4 and R 5 has a total of 7 carbon atoms, and M nmay be in the range of 5 kDa to 10,000 kDa. Furthermore, in one or more specific embodiments, the vinyl carbonyl of formula (II) may be used in combination with vinyl acetate.

[0020] Examples of branched vinyl esters include those with the following chemical structure:

[0021] [ka]

[0022] The monomer may include a monomer having the formula:

[0023] In one or more embodiments, the polymer composition may include polymers formed from monomers derived from petroleum and / or renewable resources.

[0024] In one or more embodiments, the branched vinyl ester may comprise a mixture of monomers and comonomers containing vinyl esters such as neononanoic acid, neodecanoic acid, etc. In some embodiments, the branched vinyl ester may comprise the Versatic™ Acid series tertiary carboxylic acids, such as Versatic™ Acid EH, Versatic™ Acid 9, and Versatic™ Acid 10, prepared by Koch synthesis, commercially available from Hexion™ Chemicals. In one or more embodiments, the polymer composition may comprise a polymer formed from monomers derived from petroleum and / or renewable resources.

[0025] Copolymers or terpolymers comprising branched vinyl ester monomers according to the present disclosure may have a proton nuclear magnetic resonance (NMR) content ranging from a lower limit selected from one of 40%, 45%, 50%, 55%, 60%, 65%, 70%, and 75% by weight to an upper limit selected from one of 75%, 80%, 85%, 90%, 95%, 99%, or 99.9% by weight. 1 H NMR) and carbon-13 nuclear magnetic resonance (13 The range may include the weight percent of ethylene as measured by C NMR, and any lower limit may be paired with any upper limit.

[0026] The copolymer or terpolymer comprising branched vinyl ester monomers according to the present disclosure ranges from a lower limit selected from one of 0.01%, 0.1%, 1%, 5%, 10%, 20%, or 30% by weight to an upper limit selected from 30%, 35%, 40%, 45%, 50%, 55%, or 60% by weight. 1 H NMR and 13 It may include the weight percent of vinyl ester monomers, such as those of Formula (I) and Formula (II) above, as measured by C NMR, and any lower limit may be paired with any upper limit.

[0027] In some embodiments, copolymers or terpolymers comprising branched vinyl ester monomers according to the present disclosure optionally range from a lower limit selected from one of 0%, 0.01%, 0.1%, 1%, 5%, 10%, 20%, 25%, or 30% by weight, to an upper limit selected from 30%, 35%, 40%, 45%, 50%, 55%, or 59.99% by weight. 1 H NMR and 13 The range may include the weight percent of vinyl acetate as measured by C NMR, and any lower limit may be paired with any upper limit. For polymer samples containing vinyl acetate and vinyl ester monomers, 1 Because H NMR contains substantial overlap in both the carbonyl and alkyl regions for accurate integration, contamination is quantitative. 13 Evidence of branched vinyl ester and vinyl acetate contamination can be determined using C NMR. 13 It is observed in both the carbonyl region (170-180 ppm) and the alkyl region (0-50 ppm) in the C NMR spectrum (TCE-D2, 393.1 K, 125 MHz). 1The H NMR spectrum (TCE-D2, 393.2 K, 500 MHz) shows peaks for vinyl acetate and branched vinyl esters (4.7-5.2 ppm) and ethylene (1.2-1.5 ppm), as well as additional peaks in the alkyl region (0.5-1.5 ppm) suggesting long alkyl chains in the branched vinyl ester monomers. 1 H NMR spectrum and 13 The relative intensities of the peaks found in the C NMR spectra are used to calculate the monomer incorporation of branched vinyl esters and vinyl acetate in the copolymers / terpolymers.

[0028] Copolymers or terpolymers comprising branched vinyl ester monomers according to the present disclosure have a number average molecular weight (M), as measured by gel permeation chromatography (GPC), ranging from a lower limit selected from one of 1 kDa, 5 kDa, 10 kDa, 15 kDa, and 20 kDa to an upper limit selected from one of 40 kDa, 50 kDa, 100 kDa, 300 kDa, 500 kDa, 1000 kDa, 5000 kDa, and 10000 kDa. n ) (kilodaltons (kDa)), and any lower limit can be paired with any upper limit.

[0029] Copolymers or terpolymers comprising branched vinyl ester monomers according to the present disclosure have a weight average molecular weight (M), as measured by GPC, ranging from a lower limit selected from one of 1 kDa, 5 kDa, 10 kDa, 15 kDa, and 20 kDa to an upper limit selected from one of 40 kDa, 50 kDa, 100 kDa, 200 kDa, 300 kDa, 500 kDa, 1000 kDa, 2000 kDa, 5000 kDa, 10000 kDa, and 20000 kDa. w ) (kilodaltons (kDa)), and any lower limit can be paired with any upper limit.

[0030] Copolymers or terpolymers comprising branched vinyl ester monomers according to the present disclosure may have a molecular weight distribution (M) as measured by GPC having a lower limit of any of 1, 1.5, 2, 5, or 10 and an upper limit of any of 20, 30, 40, 50, or 60. w M n and any lower limit may be paired with any upper limit.

[0031] GPC analysis may be performed on a gel permeation chromatograph coupled with triple detection, equipped with an infrared detector IR5 and a 4-bridge capillary viscometer, both from PolymerChar, and an 8-angle light scattering detector from Wyatt. A 4-column, mixed-bed, 13 μm set from Tosoh may be used at a temperature of 140° C. Experiments may be performed under the following conditions: concentration 1 mg / mL, flow rate 1 mL / min, dissolution temperature 160° C. and dissolution time 90 min, respectively, and injection volume 200 μL. The solvent used was TCB (trichlorobenzene) stabilized with 100 ppm BHT.

[0032] In one or more embodiments, copolymers or terpolymers comprising branched vinyl ester monomers according to the present disclosure can be prepared by polymerizing ethylene and one or more branched vinyl ester monomers, and optionally a vinyl acetate comonomer, in a reactor, as described, for example, in U.S. Patent Application Publication No. 2021 / 0102014, the entire contents of which are incorporated herein by reference. The method of reacting the comonomer in the presence of a radical initiator may include any suitable method in the art, such as solution phase polymerization, radical polymerization under pressure, bulk polymerization, emulsion polymerization, and suspension polymerization. In some embodiments, the reactor may be a batch autoclave reactor at a temperature below 150°C and a pressure below 500 bar, known as a low-pressure polymerization system. In some embodiments, the comonomer and one or more free-radical polymerization initiators are polymerized in a continuous or batch mode at a temperature above 150°C and a pressure above 1000 bar, known as a high-pressure polymerization system. Copolymers and terpolymers produced under high pressure conditions may have a number average molecular weight of 5 kDa to 40 kDa, a weight average molecular weight of 5 kDa to 400 kDa, and an MWD of 2 to 10.

[0033] In one or more embodiments, the reaction is carried out in a low-pressure polymerization process in which ethylene and one or more branched vinyl ester monomers, and optionally vinyl acetate comonomer, are polymerized in the liquid phase of an inert solvent and / or one or more liquid monomers. In one embodiment, the polymerization includes a free-radical polymerization initiator in an amount of from about 0.001 millimole to about 0.01 millimole, calculated as the total amount of one or more initiators for free-radical polymerization, per liter of polymerization zone volume. The amount of ethylene in the polymerization zone will be determined primarily by the total reactor pressure, which may range from about 20 bar to about 100 bar, and the temperature, which may range from about 20° C. to about 125° C. The liquid phase of the polymerization process according to the present disclosure may comprise ethylene, one or more branched vinyl ester monomers, and optionally a vinyl acetate comonomer, an initiator for free radical polymerization, and optionally one or more inert solvents, such as tetrahydrofuran (THF), chloroform, dichloromethane (DCM), dimethyl sulfoxide (DMSO), dimethyl carbonate (DMC), hexane, cyclohexane, ethyl acetate (EtOAc), acetonitrile, toluene, xylene, ether, dioxane, dimethylformamide (DMF), benzene, or acetone. Copolymers and terpolymers produced under low-pressure conditions may exhibit number-average molecular weights of 2 kDa to 20 kDa, weight-average molecular weights of 4 kDa to 100 kDa, and MWDs of 2 to 5.

[0034] additives In one or more embodiments, the polymer composition according to the present disclosure may include one or more additives such as, but not limited to, a grafting agent, an adhesion promoter, a primary antioxidant, a secondary antioxidant, an acid scavenger, a pigment, an antifog agent, an antistatic agent, a processing aid, an antiblock agent, a clarifier, a nucleating agent, a light stabilizer, a UV absorber, a heat stabilizer, a plasticizer, a rubber, an elastomer, a filler, and combinations thereof.

[0035] Grafting Agent The polymer compositions according to the present disclosure may also include at least one grafting agent, which may include one or more molecules (e.g., organic peroxides or azo initiators) capable of generating free radicals during polymer processing to enable grafting reactions with molecules containing desired functional groups. In one or more embodiments, the peroxide may include a difunctional peroxide, such as benzoyl peroxide; dicumyl peroxide; di-tert-butyl peroxide; OO-Tert-amyl-O-2-ethylhexyl monoperoxycarbonate; tert-butylcumyl peroxide; tert-butyl 3,5,5-trimethylhexanoate peroxide; tert-butyl peroxybenzoate; 2-ethylhexyl carbonate tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxide); butyl 4,4-di(tert-butylperoxide)valerate; di(2,4-dichlorobenzoyl)peroxide; di(4-methylbenzoyl)peroxide; di(tert-butylperoxyisopropyl)benzene peroxide; and the like.

[0036] Peroxides include benzoyl peroxide, 2,5-di(cumylperoxy)-2,5-dimethylhexane, 2,5-di(cumylperoxy)-2,5-dimethylhexyne-3,4-methyl-4-(t-butylperoxy)-2-pentanol, butyl-peroxy-2-ethyl-hexanoate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, t-butyl-peroxy-benzoate, t-butyl-peroxy-2-ethyl-hexanoate, 4-methyl-4-(t-amylperoxy)-2-pentanol, 4-methyl 4-(cumylperoxy)-2-pentanol, 4-methyl-4-(t-butylperoxy)-2-pentanone, 4-methyl-4-(t-amylperoxy)-2-pentanone, 4-methyl-4-(cumylperoxy)-2-pentanone, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-amylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(t-amylperoxy)hexyne-3, 2,5-dimethyl-2- t-Butylperoxy-5-hydroperoxyhexane, 2,5-dimethyl-2-cumylperoxy-5-hydroperoxyhexane, 2,5-dimethyl-2-t-amylperoxy-5-hydroperoxyhexane, m / p-alpha,alpha-di[(t-butylperoxy)isopropyl]benzene, 1,3,5-tris(t-butylperoxyisopropyl)benzene, 1,3,5-tris(t-amylperoxyisopropyl)benzene, 1,3,5-tris(cumylperoxyisopropyl)benzene, di[1,3-dimethyl-3-(t- butylperoxy)butyl]carbonate, di[1,3-dimethyl-3-(t-amylperoxy)butyl]carbonate, di[1,3-dimethyl-3-(cumylperoxy)butyl]carbonate, di-t-amyl peroxide, t-amyl cumyl peroxide, t-butyl-isopropenylcumyl peroxide, 2,4,6-tri(9-eptane9nyl)-s-triazine, 1,3,5-tri[1-(t-butylperoxy)-1-methylethyl]benzene, 1,3,5-tri-[(t-butylperoxy)-isopropyl]benzene, 1,3-Dimethyl-3-(t-butylperoxy)butanol, 1,3-dimethyl-3-(t-amylperoxy)butanol, di(2-phenoxyethyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, dimyristyl peroxydicarbonate, dibenzyl peroxydicarbonate, di(isobomyl)peroxydicarbonate, 3-cumylperoxy-1,3-dimethylbutyl methacrylate, 3-t-butylperoxy-1,3-dimethylbutyl methacrylate , 3-t-amylperoxy-1,3-dimethylbutyl methacrylate, tri(1,3-dimethyl-3-t-butylperoxybutyloxy)vinylsilane, 1,3-dimethyl-3-(t-butylperoxy)butyl N-[1-{3-(1-methylethenyl)-phenyl)1-methylethyl]carbamate, 1,3-dimethyl-3-(t-amylperoxy)butyl N-[1-{3(1-methylethenyl)-phenyl}-1-methylethyl]carbamate, 1,3-dimethyl-3-(cumylperoxy))butyl N-[1-{3-(1-methyl ethylethenyl)-phenyl}-1-methylethyl]carbamate, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, n-butyl 4,4-di(t-amylperoxy)valerate, ethyl 3,3-di(t-butylperoxy)butyrate, 2,2-di(t-amylperoxy)propane, 3,6,6,9,9-pentamethyl-3-ethoxycarbonylmethyl-1,2,4,5-tetraoxacyclononane, n-butyl-4,4-bis(t-butylperoxy) oxy)valerate, ethyl-3,3-di(t-amylperoxy)butyrate, benzoyl peroxide, OO-t-butyl-O-hydrogen-monoperoxy-succinate, OO-t-amyl-O-hydrogen-monoperoxy-succinate, 3,6,9,triethyl-3,6,9-trimethyl-l,4,7-triperoxynonane (or methyl ethyl ketone peroxide cyclic trimer), methyl ethyl ketone peroxide cyclic dimer, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane, 2,5-dimethyl-2,5-Di(benzoylperoxy)hexane, t-butyl perbenzoate, t-butyl peroxyacetate, t-butylperoxy-2-ethylhexanoate, t-amyl perbenzoate, t-amyl peroxyacetate, t-butylperoxyisobutyrate, 3-hydroxy-1,1-dimethyl t-butylperoxy-2-ethylhexanoate, OO-t-amyl-O-hydrogen-monoperoxysuccinate, OO-t- Butyl-O-hydrogen-monoperoxysuccinate, di-t-butyl diperoxyphthalate, t-butylperoxy(3,3,5-trimethylhexanoate), 1,4-bis(t-butylperoxycarbo)cyclohexane, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl-peroxy-(cis-3-carboxy)propionate, allyl 3-methyl-3-t-butylperoxybutyrate, OO- t-Butyl-O-isopropyl monoperoxycarbonate, OO-t-butyl-O-(2-ethylhexyl) monoperoxycarbonate, 1,1,1-tris[2-(t-butylperoxycarbonyloxy)ethoxymethyl]propane, 1,1,1-tris[2-(t-amylperoxycarbonyloxy)ethoxymethyl]propane, 1,1,1-tris[2-(cumylperoxycarbonyloxy)ethoxymethyl]propane Also included may be mentioned peroxypropane, OO-t-amyl-O-isopropyl monoperoxycarbonate, di(4-methylbenzoyl)peroxide, di(3-methylbenzoyl)peroxide, di(2-methylbenzoyl)peroxide, didecanoyl peroxide, dilauroyl peroxide, 2,4-dibromo-benzoyl peroxide, succinic peroxide, dibenzoyl peroxide, di(2,4-dichloro-benzoyl)peroxide, and combinations thereof.

[0037] The amount of grafting agent (or the amount of free radical generator itself, if only the active ingredient is considered) may range from a lower limit of 0.001, 0.01, 0.1, or 0.5 parts by weight per 100 phr of rubber / resin (phr) to an upper limit of 1, 2, or 3, relative to 100 phr of polymer, any lower limit being usable in combination with any suitable upper limit. In one or more embodiments, the grafting agent may be in an amount ranging from 0.001 phr to 2 phr, or even from 0.01 phr to 1 phr.

[0038] Adhesion promoter Functional groups can be grafted onto polymers for tie layer materials to ensure reactive adhesion with certain polymers in multilayer constructions. To improve adhesion, unsaturated molecules such as maleic anhydride, acrylic acid, methacrylic acid, glycidyl methacrylate, maleic acid, fumaric acid, tetrahydrophthalic anhydride, citraconic anhydride, itaconic anhydride, (2-dodecen-1-yl)succinic anhydride, or similar molecules containing carboxylic acids, anhydrides, epoxides, etc., can be grafted onto the polymers described herein by the use of free radicals (e.g., using organic peroxides or azo initiators).

[0039] The amount of adhesion promoter may range from lower limits of 0.01, 0.05, 0.1, 0.5, 1.0, 2.0, or 4.0 parts by weight per 100 rubber / resin (phr) to upper limits of 6.0, 8.0, 10.0, 12.0, or 15.0 parts by weight per 100 phr of polymer, any lower limit may be used in combination with any suitable upper limit. In one or more embodiments, the UV absorber may be in an amount ranging from 0.1 phr to 15 phr.

[0040] antioxidants In one or more embodiments, the polymer composition according to the present disclosure may include one or more antioxidants. The polymer composition according to an embodiment may include at least a first antioxidant and a second antioxidant. The antioxidants according to the present disclosure may include monophenol-type antioxidants, bisphenol-type antioxidants, polymeric phenol-type antioxidants, sulfur-containing antioxidants, and phosphite-type antioxidants.

[0041] Monophenolic antioxidants include, inter alia, 2,6-di-tert-butyl-p-cresol, butylhydroxyanisole, and 2,6-di-tert-butyl-4-ethylphenol. Bisphenolic antioxidants include 2'-methylenebis(4-methyl-6-tert-butylphenol), 2'-methylenebis(4-ethyl-6-tert-butylphenol), 4'-thiobis(3-methyl-6-tert-butylphenol), 4'-butylidenebis(3-methyl-6-tert-butylphenol), and 3,9-bis(1,1-dimethyl-2-R-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxyethyl)}2,4,9,10-tetroxaspiro-5,5-undecane. Polymeric phenolic antioxidants include 1,1,3-tris(2- methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis-methylene-3-('',''-di-tert-butyl-''-hydroxyphenyl)propionate methane, bis{(3,''-bis-''-hydroxy-''-tert-butylphenyl)butyric acid glucose ester, 1,3,5-tris('',''-di-tert-butyl-''-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione, and triphenol (vitamin E).

[0042] Sulfur-containing antioxidants include dilauroyl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiopropionate.

[0043] Phosphite-type antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4'',-butylidene-bis(3-methyl-6-tert-butylphenyl-ditridecyl) phosphite, cyclic neopentane-tetraylbis(octadecyl) phosphite, tris(mono and / or di)phenyl phosphite, diisodecyl pentaerythritol 12eptane 12nyle, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- Examples include (3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, cyclic neopentane-tetraylbis(2,4-di-tert-butylphenyl)phosphite, cyclic neopentane-tetraylbis(2,6-di-tert-methylphenyl)phosphite, and 2,2-methylenebis(4,6-tert-butylphenyl)octylphosphite.

[0044] In one or more embodiments, phenolic and phosphite type antioxidants may be used alone or, preferably, in combination to increase thermal stability.

[0045] The amount of antioxidant added may range from a lower limit of 0.001, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 1, or 2 parts by weight per 100 rubber / resin (phr) to 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5 parts by weight per 100 phr of polymer, any lower limit being combinable with any suitable upper limit. In one or more embodiments, the antioxidant may be in an amount ranging from 0.002 phr to 1 phr.

[0046] Acid Scavenger Acid scavengers, such as zinc stearate, zinc oxide, calcium stearate, dihydrotalcite, and other acid scavengers known in the art, may be added to the aforementioned compositions to, among other things, neutralize potential catalyst residues.

[0047] The amount of acid scavenger added can range from a lower limit of 0.001, 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 1, or 2 parts by weight per 100 rubber / resin (phr) to 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5 parts by weight per 100 phr of polymer, any lower limit being combinable with any suitable upper limit. In one or more embodiments, the scavenger can be in an amount ranging from 0.002 phr to 1 phr.

[0048] Processing aids Processing aids such as fluoropolymers and fluoroelastomers, e.g., the Viton™ series, thermoplastic elastomers based on block copolymers of diisocyanates and polyols (i.e., TPUs), polydimethysiloxanes, and other siloxanes such as ultra-high molecular weight (UHMW) polydimethysiloxanes, can be added to the described formulations to improve processability, avoid melt fracture, and thus enable faster line speeds.

[0049] The amount of processing aid added can range from a lower limit of 0.001, 0.005, 0.01, 0.1, 0.2, 0.3, 0.4, or 0.5 parts by weight per 100 rubber / resin (phr) to 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5 parts by weight per 100 phr of polymer, any lower limit being combinable with any suitable upper limit. In one or more embodiments, the processing aid can be added in an amount ranging from 0.002 phr to 1 phr.

[0050] Anti-blocking agent Inorganic antiblocking agents, such as silica (natural or synthetic), talc, calcium carbonate, ceramic spheres (e.g., alumina, alumina silicate, etc.), clay, mica; organic antiblocking agents, such as bis-amides, primary and secondary amides (e.g., erucamides), organic and metallic stearates, silicone, PTFE, waxes (e.g., paraffin wax), and other antiblocking agents known in the art. Antiblocking agents may be added primarily to prevent blocking (i.e., adhesion of two adjacent thin films) by creating fine protrusions on the thin film surface to reduce interactions (e.g., van der Waals forces) between the surfaces of the thin films.

[0051] The amount of antiblock agent added can range from a lower limit of 0.001, 0.005, 0.01, 0.1, 0.2, 0.3, 0.4, or 0.5 parts by weight per 100 rubber / resin (phr) to 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5 parts by weight per 100 phr of polymer, any lower limit being combinable with any suitable upper limit. In one or more embodiments, the processing aid can be added in an amount ranging from 0.002 phr to 1 phr.

[0052] antistatic agent To manage electrostatic charges during polymer processing and use, and to control charge accumulation on the surface of polymers through some specific mechanisms, for example, using molecules containing charge structures, lone electron pairs, or hygroscopic groups (which can interact with and bind to moisture present in the atmosphere), organic antistatic agents, such as phosphates (usually K or Na salts of the corresponding free acid), quaternary amines, nonionic hygroscopic materials (i.e., ethylene oxide or propylene oxide surfactants), sulfate compounds or sulfonated compounds, as well as conductive fillers and additives, such as carbon black, conductive fibers (e.g., carbon, steel, cellulose), graphite, flake metal powders, carbon nanotubes, intrinsically conductive polymers (ICPs), and other antistatic agents known in the art, can be added to the formulations of the present invention. Dissipating these charges can prevent problems such as attracting dust and other contaminants, static electricity accumulation and static electricity discharge (which can avoid sparks, electric shocks, etc.), paint and print defects, and fires or explosions in flammable or explosive environments.

[0053] The amount of antistatic agent added can range from a lower limit of 0.001, 0.005, 0.01, 0.1, 0.2, 0.3, 0.4, or 0.5 to 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5 parts by weight per 100 rubber / resin (phr) per 100 phr of polymer, any lower limit being combinable with any suitable upper limit. In one or more embodiments, the antistatic agent can be added in an amount ranging from 0.002 phr to 1 phr.

[0054] Anti-fogging agent To increase the wettability of the polymer and avoid caking and disturbance of light transmission, non-ionic anti-fog agents may be added, such as ethoxylated alkylamines, sorbitan esters, polyglycerol stearates, and glycerol sorbitan esters, more particularly glycerol esters (GE), octadecanoic acid (OA), polyglycerol esters (PE), polyglycerol stearates; 1,2,3-propanetriol (PS), polyglycerol monostearate (PM), sorbitan monostearate (SM), glyceryl monooleate (GM), and other anti-fog agents known in the art.

[0055] The amount of antifog agent added can range from a lower limit of 0.001, 0.005, 0.01, 0.1, 0.2, 0.3, 0.4, or 0.5 to 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5 parts by weight per hundred rubber / resin (phr) per hundred phr of polymer, any lower limit being combinable with any suitable upper limit. In one or more embodiments, the processing aid can be added in an amount ranging from 0.002 phr to 1 phr.

[0056] Light stabilizers The use of light stabilizers (LS), especially hindered amine-type (HALS), when combined with UV absorbers, produces significant synergistic effects. Other typical LS compounds can function equally well as HALS, but many of them cause color in polymer compounds and are therefore undesirable for use in solar cell encapsulants. Hindered amine-type light stabilizers are generally secondary amines, tertiary amines, acetylated amines, N-hydrocarbyloxy-substituted amines, hydroxy-substituted amines, or other substituted cyclic amines with a significant amount of steric hindrance.In particular, light stabilizers include molecules such as dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensates, poly(6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)iminohexamethylene{{2,2,6,6-tetramethyl-4- Piperidylimino, N,''-bis(3-aminopropyl)ethylenediamine-2,4-bis(N-butyl-N-(1.2.2.6,6-pentamethyl-4-piperidyl)amino-6-chloro-1,3,5-triazine condensate, bis(2.2.6,6-tetramethyl-4-piperidyl)sebacate, bis(1.2.2.6,6-pentamethyl-4-piperidyl)2-(3,5-di-tert-4-hydro (roxybenzyl)-2-n-butylmalonate, propanedioic acid, C4-(methoxyphenyl)-methylene-, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, polymethylpropyl-3-oxy-4-(2,2,6,6-tetramethyl)piperidinylsiloxane, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)-2,5-pyrrolidinedione, 1, 3,5-Triazine-2,4,6-triamine, N,''-1,2-ethanediylbis(4,6-bisbutyl(1,2,2,6,6-pentamethyl-4-eptane15nyly)amino-1,3,5-triazin-2-yl)imino-3,1propanediyl)-bis'',''-dibutyl-'',''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-(Chimassorb 119, CAS Registry Number 106990-43-6); a polymer containing N,''-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine, 2,4,6-trichloro-1,3,5-triazine, and 2,4,4-trimethyl-1,2-pentamine (Chimassorb 944, ACS Registry Number 70624-18-9); and a polymer of N,''-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with 2,4,6-trichloro-1,3,5-triazine and tetrahydro-1,4-oxazine.

[0057] The amount of light stabilizer may range from a lower limit of 0.001 phr, 0.01 phr, or 0.1 phr to an upper limit of 0.2 phr, 1 phr, 3 phr, or 5 phr, per 100 phr of polymer, and any lower limit may be used in combination with any suitable upper limit. In one or more embodiments, the light stabilizer may be present in an amount ranging from 0.002 phr to 1 phr.

[0058] UV absorber Any known UV absorber may be utilized within the present disclosure. General classes of preferred UV absorbers are benzophenones, benzotriazoles, triazines, salicylates, hydroxybenzophenones, hydroxyphenyltriazines, esters of substituted and unsubstituted benzoic acids, and the like, and mixtures thereof.

[0059] Specific benzophenone UV absorbers include, for example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2,4-dihydroxybenzophenone, 2,''-dihydroxy-4-methoxybenzophenone, 2,''-dihydroxy-4,''-dimethoxybenzophenone, and 2,'',4,''-tetrahydroxybenzophenone.

[0060] Benzotriazole UV absorbers include hydroxyphenyl-substituted benzotriazole compounds such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy5-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dimethylphenyl)benzotriazole, 2-(2-methyl-4-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-3-methyl-5-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-amylphenyl)benzotriazole, and 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole.

[0061] Triazine UV absorbers include 2-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, etc. Salicylate UV absorbers include phenyl salicylate and p-octylphenyl salicylate.

[0062] The amount of UV absorber may range from a lower limit of 0.001, 0.01, 0.1, 0.2, 0.3, 0.4, or 0.5 to an upper limit of 0.5, 1.0, 2.0, 3.0, 4.0, or 5.0 parts by weight per 100 rubber / resin (phr) per 100 phr of polymer, any lower limit may be used in combination with any suitable upper limit. In one or more embodiments, the UV absorber may be in an amount ranging from 0.002 phr to 1 phr.

[0063] heat stabilizer Heat stabilizers can be used as optional additives in solar cell encapsulants to protect the polymer, especially during processing, especially during the curing stage. Any conventional heat stabilizer can be used, including but not limited to phenolic antioxidants, alkylated monophenols, alkylthiomethylphenols, hydroquinones, alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, O-benzyl compounds, N-benzyl compounds, and S-benzyl compounds, hydroxybenzylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, amine antioxidants, arylamines, diarylamines, polyarylamines, acylaminophenols, oxamides, metal deactivators, phosphites, phosphonites, benzyl phosphonates, ascorbic acid (vitamin C), peroxide deactivators, hydroxylamines, nitrones, thiosynergists, benzofuranones, indolinones, and mixtures thereof. Its use is optional and in some cases is undesirable (especially when it severely suppresses crosslinking).

[0064] The heat stabilizer may range from a lower limit of 0.001 phr, 0.01 phr, 0.1 phr, or 0.2 phr to an upper limit of 1 phr, 2 phr, 3 phr, 4 phr, or 5 phr, per 100 phr of polymer, and any lower limit may be used in combination with any suitable upper limit. In one or more embodiments, the heat stabilizer may be in an amount ranging from 0.002 phr to 1 phr.

[0065] plasticizer The polymer compositions according to the present disclosure may contain one or more plasticizers to adjust the physical properties and processability of the composition. In some embodiments, plasticizers according to the present disclosure include bis(2-ethylhexyl) phthalate (DEHP), di-isononyl phthalate (DINP), bis(n-butyl) phthalate (DNBP), butyl benzyl phthalate (BZP), di-isodecyl phthalate (DIDP), di-n-octyl phthalate (DOP or DNOP), di-o-octyl phthalate (DIOP), diethyl phthalate (DEP), di-isobutyl phthalate (DIBP), di-n-hexyl phthalate, tri-methyl trimellitate (TMTM), tri-(2-ethylhexyl) trimellitate (TEHTM-MG), tri-(n-octyl, n-decyl) trimellitate, tri-(heptyl, nonyl) trimellitate, n-octyl trimellitate, among other plasticizers and polymeric plasticizers. Polyesters of adipic acid such as bis(2-ethylhexyl) adipate (DEHA), dimethyl adipate (DMD), mono-methyl adipate (MMAD), dioctyl adipate (DOA), dibutyl sebacate (DBS), VIERNOL, dibutyl maleate (DBM), di-isobutyl maleate (DIBM), benzoates, epoxidized soybean oil and derivatives, n-ethyltoluenesulfonamide, n-(2-hydroxypropyl)benzenesulfonamide, n-(n-butyl)benzenesulfonamide, tricresyl phosphate (TCP), tributyl phosphate (TBP), glycols / polyesters, triethylene glycol dihexanoate (3gh), tetraethylene glycol diheptanoate, polybutene, acetylated monoglycerides;Included may be one or more of alkyl citrate, triethyl citrate (TEC), acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, trioctyl citrate, acetyl trioctyl citrate, trihexyl citrate, acetyl trihexyl citrate, butyryl trihexyl citrate, trihexyl o-butyryl citrate, trimethyl citrate, alkyl sulfonic acid phenyl ester, 2-cyclohexanedicarboxylic acid di-isononyl ester, nitroglycerin, butanetriol trinitrate, dinitrotoluene, trimethylolethane trinitrate, diethylene glycol dinitrate, triethylene glycol dinitrate, bis(2,2-dinitropropyl) formal, bis(2,2-dinitropropyl) acetal, 2,2,2-trinitroethyl 2-nitroxyethyl ether, mineral oil, vegetable oil, or bio-based oil. In certain embodiments, one of the one or more plasticizers may be mineral oil;

[0066] The polymer composition according to the present disclosure may optionally include a plasticizer in an amount ranging from 0 phr to 20 phr. The plasticizer can be present in an amount ranging from a lower limit of one of 0 phr, 1.0 phr, 2.0 phr, 5.0 phr, 8.0 phr, and 10.0 phr to an upper limit of one of 12 phr, 15 phr, 18 phr, 19 phr, and 20 phr, any lower limit being combinable with any suitable upper limit.

[0067] Nucleating and Clarifying Agents The polymer composition according to the present disclosure may contain one or more nucleating and / or clarifying agents, such as metal hexahydrophthalates, benzoates, stearates, organic phosphates, bisamides, sorbitol, metal carboxylates, metal aromatic carboxylates, polymeric agents, talc, clays, inorganic oxide particles and nanoparticles, and mixtures of the above chemicals. Examples of sorbitol include, but are not limited to, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, and 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol. Acid metal salts include, but are not limited to, disodium salt of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, a mixture of zinc stearate and calcium salt of 1,2-cyclohexanedicarboxylic acid, and disodium salt of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid. Other compounds include, but are not limited to, disodium bicyclo[2.2.1]18eptanedicarboxylate, bisamides, lithium carbonate, benzoic acid, nano-zinc oxide, talc, clays, powdered polymeric agents, polyphenylene oxide, polyvinylene difluoride, polycarbonate, polycarbonate-siloxane copolymer, crosslinked polycarbonate, polyetherimides, polyamides, ethylene propylene diene monomer, polyoxymethylene, and other suitable nucleating and clarifying agents known in the art.

[0068] The amount of nucleating and / or clarifying agent added may range from a lower limit of 0.001, 0.005, 0.01, 0.1, 0.2, 0.3, 0.4, or 0.5 to 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, or 5 parts by weight per 100 rubber / resin (phr) per 100 phr of polymer, any lower limit being combinable with any suitable upper limit. In one or more embodiments, the nucleating and / or clarifying agent may be added in an amount ranging from 0.002 phr to 1 phr.

[0069] Tie Layer As previously mentioned, the thin films of the present disclosure can be used as tie layers to join two different materials together.

[0070] A tie layer film according to one or more embodiments may comprise a polymer (copolymer or terpolymer) having a total comonomer content (branched vinyl ester and optional vinyl acetate) ranging from a lower limit selected from one of 0.1%, 1%, 5%, 10%, 20%, 25%, or 30% by weight to an upper limit selected from 30%, 35%, 40%, 45%, 50%, 55%, or 60% by weight, any lower limit being combinable with any suitable upper limit.

[0071] The tie layer film according to one or more embodiments has a coating density of 0.8 g / cm 3 , 0.9g / cm 3 , 0.905g / cm 3 , 0.91g / cm 3 , 0.915g / cm 3 , 0.92g / cm 3 , 0.925g / cm 3 , 0.93g / cm 3 0.95 g / cm 3 , 0.955g / cm 3 , 0.96g / cm 3 , 0.965g / cm 3 , 0.97g / cm 3 , 0.98g / cm 3, 0.99g / cm 3 , 1.0g / cm 3 , 1.1g / cm 3 , 1.2g / cm 3 , or 1.3 g / cm 3 to an upper limit selected from one of the following, any lower limit can be combined with any suitable upper limit.

[0072] A tie layer film according to one or more embodiments may comprise a polymer (copolymer or terpolymer) having a melt index (I2), as measured according to ASTM D1238 (190°C and 2.16 kg load), ranging from a lower limit of 0.01 g / 10 min, 0.1 g / 10 min, 0.5 g / 10 min, 1 g / 10 min, 2 g / 10 min, 5 g / 10 min, 10 g / 10 min, 15 g / 10 min, 20 g / 10 min, 30 g / 10 min, 40 g / 10 min, or 50 g / 10 min, to an upper limit of 50 g / 10 min, 60 g / 10 min, 70 g / 10 min, 80 g / 10 min, 90 g / 10 min, or 100 g / 10 min, any lower limit can be combined with any suitable upper limit.

[0073] A tie layer film according to one or more embodiments may have a thickness ranging from a lower limit of 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 10 μm, 15 μm, 20 μm, 30 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, or 500 μm to an upper limit of 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1000 μm, any lower limit being combinable with any suitable upper limit.

[0074] In addition to the copolymer or terpolymer described herein, thin films for use as tie layers may include one or more of the following: a grafting agent in an amount of 0.01 phr to 1 phr; an adhesion promoter in an amount of 0.01 phr to 15 phr; a first antioxidant in an amount of 0.002 phr to 1 phr; a second antioxidant in an amount of 0.002 phr to 1 phr; a light stabilizer in an amount of 0.002 phr to 1 phr; a UV absorber in an amount of 0.002 phr to 1 phr; an acid scavenger in an amount of 0.002 phr to 1 phr; a processing aid in an amount of 0.002 phr to 1 phr; or optionally, one or more additives selected from the group including pigments, antifog agents, antistatic agents, antiblocking agents, clarifiers, nucleating agents, heat stabilizers, plasticizers, rubbers, elastomers, fillers, and combinations thereof.

[0075] In one or more embodiments, a thin film suitable for use as a tie layer has a coating density of 0.91 g / cm 3 , 0.915g / cm 3 , 0.92g / cm 3 , 0.925g / cm 3 , 0.93g / cm 3 0.95 g / cm 3 , 0.955g / cm 3 , 0.96g / cm 3 , 0.965g / cm 3 , or 0.97 g / cm 3 to an upper limit selected from one of the following: 0.92 g / cm 3 ~0.96g / cm 3 The density may range from .gtoreq. ...

[0076] In one or more embodiments, thin films suitable for use as tie layers have ASTM DSC values ​​ranging from a lower limit of 0.01 g / 10 min, 0.1 g / 10 min, 0.2 g / 10 min, 0.3 g / 10 min, 0.4 g / 10 min, 0.5 g / 10 min, 1 g / 10 min, 2 g / 10 min, 5 g / 10 min, 10 g / 10 min, 15 g / 10 min, 20 g / 10 min, 25 g / 10 min, 30 g / 10 min, 40 g / 10 min, or 50 g / 10 min, to an upper limit of 50 g / 10 min, 60 g / 10 min, 70 g / 10 min, 80 g / 10 min, 90 g / 10 min, 100 g / 10 min, 150 g / 10 min, or 200 g / 10 min. The polymer may include a polymer having a melt index (I2) measured according to D1238 (190°C and 2.16 kg load), and any lower limit can be combined with any suitable upper limit. In one or more embodiments, the polymer may have a melt index (I2) in the range of 0.1 g / 10 min to 100 g / 10 min, or even in the range of 0.2 g / 10 min to 25 g / 10 min.

[0077] In one or more embodiments, thin films suitable for use as tie layers may include polymers having a total comonomer content ranging from a lower limit of 0.1%, 1%, 2%, 5%, or 10% by weight to an upper limit of 11%, 20%, 30%, 40%, 50%, or 60% by weight, any lower limit being combinable with any suitable upper limit.

[0078] In one or more embodiments, a thin film suitable for use as a tie layer may comprise a polymer having a melting point, as measured according to ASTM D3418, ranging from a lower limit of 30° C., 40° C., 50° C., or 60° C. to an upper limit of 60° C., 70° C., 90° C., 100° C., or 120° C., any lower limit being combinable with any suitable upper limit. In one or more embodiments, the polymer may comprise a melting point below 120° C., or a melting point in the range of 60° C. to 100° C.

[0079] In one or more embodiments, thin films suitable for use as tie layers may include polymers having a contact angle, measured according to ASTM D5946, of greater than 70°, or greater than 75°, or greater than 80°, or greater than 85°, or greater than 90°.

[0080] In one or more embodiments, a thin film suitable for use as a tie layer has a viscosity of 25000 μm.g / m 2 Less than .day, 24000μm.g / m 2 Less than .day, 23000μm.g / m 2 .day, less than 22000μm.g / m 2 Less than .day, 21000μm.g / m 2 Less than .day or 20000μm.g / m 2 The composition may have a water vapor transmission coefficient as measured in accordance with ASTM F1249 of less than .day.

[0081] In one or more embodiments, thin films suitable for use as tie layers may comprise polymer compositions that exhibit a glass transition temperature, as measured via tan δ, of less than 0°C, less than -5°C, less than -10°C, less than -15°C, less than -17°C, less than -19°C, less than -21°C, less than -23°C, or less than -25°C.

[0082] In one or more embodiments, thin films suitable for use as tie layers may comprise polymer compositions that exhibit a glass transition temperature, as measured via loss modulus, of less than 0°C, less than -5°C, less than -10°C, less than -15°C, less than -20°C, less than -25°C, less than -27°C, less than -29°C, less than -31°C, less than -33°C, or less than -35°C.

[0083] Thin film preparation method

[0010] Embodiments disclosed herein may relate to a method for preparing a thin film comprising a polymer composition according to the present disclosure. The method may include preparing a polymer composition by blending a polymer prepared from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate according to embodiments described herein, and optionally one or more of the following: a grafting agent, an adhesion promoter, a first antioxidant, a second antioxidant, an acid scavenger, a pigment, an antifog agent, an antistatic agent, a processing aid, an antiblocking agent, a clarifier, a nucleating agent, a light stabilizer, a UV absorber, a heat stabilizer, a plasticizer, a rubber / elastomer, a filler, and combinations thereof.

[0084] The blending step can be carried out by any suitable method, including using a twin-screw extruder, a single-screw extruder, a kneader, a Banbury mixer, mixing rollers, a blown or cast film extruder, or a blown extruder. The grafting reaction involves forming at least one covalent bond between the base polymers. Grafting can include, for example, melt grafting, solution grafting, or solid-state grafting. Melt grafting can be carried out in suitable equipment, such as a twin-screw extruder, a single-screw extruder, a kneader, a Banbury mixer, other internal mixers, mixing rollers, a blown or cast film extruder, a blown extruder, or the like.

[0085] The prepared polymer composition can then be used to prepare a thin film comprising the polymer composition, which can be formed as a separate structure or in combination with one or more substrates. For example, the thin film can be produced by cast film extrusion, blown film extrusion, calendering, extrusion blow molding, injection molding, injection stretch blow molding, pipe extrusion, thermoforming, or any other suitable method.

[0086] Molded product The embodiments disclosed herein may relate to a molded article comprising at least one thin film disclosed herein. The molded article may include a substrate to which the thin film is applied. The molded article may include one or more substrates rather than a single substrate. For example, the thin film may be a tie layer that bonds two different substrates together. In embodiments including two or more substrates, the thin film may be included between the two substrates as a tie layer.

[0087] In one or more embodiments, molded articles (e.g., multilayer blow molded products, multilayer pipes, multilayer films, multilayer films and sheets for food packaging) can be produced using tie layers based on the above polymer compositions, especially those comprising the copolymers or terpolymers described herein.

[0088] Method for manufacturing molded articles Embodiments disclosed herein may relate to methods of making shaped articles including thin films according to embodiments disclosed herein. The methods may include applying the thin film to a substrate, where the applying step includes co-extrusion and / or extrusion coating of the thin film with the substrate. The shaped articles may be made by cast film extrusion, blown film extrusion, extrusion blow molding, injection molding, injection stretch blow molding, pipe extrusion, thermoforming, calendering, or any method suitable for producing the desired shaped article. The methods may be used to produce multi-layer flexible packaging, as well as multi-layer extrusion blow-molded products, multi-layer extruded pipe, multi-layer thermoformed parts, and the like.

[0089] Materials, Experimental Methods, and Characterization material Compositions based on ethylene, vinyl acetate, and vinyl neodecanoate (VeoVA™ 10) were tested. Terpolymer samples DV001A and DV001B were produced in a high-pressure industrial asset normally operated to produce EVA copolymers. Typical reactor conditions for the production of the terpolymers are listed in Table 1.

[0090] [Table 1]

[0091] Evidence of branched vinyl ester and vinyl acetate contamination 13 It is found in both the carbonyl region (170 ppm to 180 ppm) and the alkyl region (0 ppm to 50 ppm) of the C NMR spectrum (TCE-D2, 393.1 K, 125 MHz). 1 The H NMR spectrum (TCE-D2, 393.2 K, 500 MHz) shows vinyl acetate and branched vinyl ester peaks (4.7 ppm to 5.2 ppm) and ethylene peaks (1.2 ppm to 1.5 ppm), as well as additional peaks in the alkyl region (0.5 ppm to 1.5 ppm) suggesting the long alkyl chains of the branched vinyl ester monomers. 1 H NMR spectrum and 13 The relative intensities of the peaks found in the C NMR spectra are used to calculate the monomer incorporation of branched vinyl esters and vinyl acetate in the copolymers / terpolymers.

[0092] Neat polymer characterization The content of VA and VeoVa™ 10 is: 1 H NMR and 13 The melting and crystallization behavior of the samples was measured by C NMR (see above). The melting and crystallization behavior of the samples was studied by DSC. The experiments were performed on a TA Instruments DSC Discovery - DSC2500 in nitrogen according to ASTM D3418. The samples were cooled from 200°C to -20°C and then heated to 200°C at a rate of 10°C / min.

[0093] Density was measured according to ASTM D792, Vicat softening point (10 N) according to ASTM D1525, hardness (Shore A) according to ASTM D2240, and contact angle according to ASTM D5946. Test specimens for density, Vicat, hardness, and contact angle measurements were prepared by compression molding according to ASTM D4703 and conditioned at 23°C and 50% RH for at least 24 hours. Melt flow rate was evaluated at 190°C and 2.16 kg according to ASTM D1239.

[0094] Thin Film Extrusion Cast films of the aforementioned polymers (neat) were produced in a Leonard OCS ME-20 / 2800-V3 cast film extruder equipped with a flat die and chilled pull roll. Prior to extrusion, the die was cleaned using a spatula and brass wool. To evaluate the processability and aesthetics of the films under these conditions, the temperature profile and melting point were limited to 140°C. Due to the strong adhesion of the EVA film to the pinch roll, the EVA film was previously covered with brown paper and cooled to approximately 9°C.

[0095] Thin film characterization The relevant properties (optical, mechanical and barrier) were tested on neat thin films of the polymer and are shown in the table below.

[0096] Optical properties (clarity, haze, and transmittance) were measured as defined by ASTM D1003, gloss (45° and 60°) was measured according to ASTM D2457, water vapor transmission rate was measured according to ASTM F1249 (37.8°C, 100 RH, 1 atm), and tensile testing was performed using an optical extensometer according to ASTM D882 (crosshead speed 500 mm / min), and stress and strain at yield and break, and secant modulus (1%) were reported.

[0097] The glass transition temperatures (T g) was determined from the measurement of the Tan δ peak maximum of the sample during DMA measurement using a TA800 DMA instrument in tensile mode. Thin films (approximately 0.5 mm) were compression molded at 150 °C and o The specimen was cooled to 30°C and its viscoelastic response was measured at a rate of 30°C while a preload of 0.01 N was applied at a frequency of 1 Hz and an amplitude of 15 μm. o The storage modulus, loss modulus, and tan δ (the ratio of storage modulus to loss modulus) were recorded as a function of temperature. [Example]

[0098] Example 1 Neat Polymer Characterization—The basic properties of the previously described terpolymers (designated DV001A, DV001B) and EVA benchmarks—Braskem SA grade HM728 and SK Chemicals Co. grade EVATANE 3345PV—are shown in Table 2.

[0099] [Table 2]

[0100] Example 2 Neat thin films were prepared according to the thin film extrusion procedure described above. The films were collected and rolled with brown paper to prevent blocking. The extrusion parameters were as follows:

[0101] [Table 3]

[0102] The films were characterized according to the methods described above. Overall, similar optical properties were observed for the terpolymers in Tables 4 and 5, with slightly higher clarity and lower haze compared to HM728. As seen in Table 6, lower water vapor transmission coefficients were observed for the terpolymers, especially DV001B, which contained the most VeoVa10 monomer.

[0103] [Table 4]

[0104] [Table 5]

[0105] [Table 6]

[0106] The glass transition temperatures were obtained for the prepared thin films according to the above method (DMA). The results are as follows:

[0107] [Table 7]

[0108] T for terpolymer g are very similar to each other, and they are comparable to the values ​​measured for EVA with 33% by weight of VA (EVATANE 3345PV), with a slightly higher value via -tan δ and a lower value via loss modulus. Both terpolymers exhibit lower T values ​​than EVA with 28% by weight of VA (HM728). g This suggests that the studied terpolymers exhibit good low-temperature flexibility.

[0109] The thermal properties of the neat samples were determined by DSC according to the method previously described.

[0110] [Table 8]

[0111] The DSC data (melting point and enthalpy of fusion and crystallization temperature and enthalpy of crystallization) demonstrated the expected trends, even though DV001B behaved similarly to HM728. Slightly lower Tm2, ​​Tc, and ΔH can be seen for DV001A compared to HM728. EVATANE 3345PV exhibited a lower melting point and enthalpy of fusion due to its higher VA content (and higher total mole % comonomer content).

[0112] Therefore, the above film properties indicate that the films according to the present disclosure have better thermal properties compared to conventional EVA copolymer HM728, including better low temperature flexibility, and better optical properties such as higher transparency and lower haze, making them suitable for use as tie layer films.

[0113] While only a few exemplary embodiments have been described in detail above, those skilled in the art will readily recognize that many modifications are possible in the exemplary embodiments without substantially departing from the present invention. Accordingly, all such modifications are intended to be included within the scope of the present disclosure, as defined by the following claims. In the claims, means-plus-function clauses are intended to cover not only the structures described herein and structural equivalents when performing the recited function, but also equivalent structures. Thus, although nails and screws may not be structurally equivalent in that nails use cylindrical surfaces to attach wooden parts together, while screws use helical surfaces in a fastening environment, nails and screws may be equivalent structures. It is applicant's express intent not to invoke 35 U.S.C. 112(f) on any limitation of the claims herein, except where the claims clearly use the term "means for" with the relevant function.

Claims

1. 1. A tie layer film comprising a polymer composition, The ethylene content ranges from 40% to 99.9% by weight, and the melt index (I) measured according to ASTM D1238 (190°C and 2.16 kg load) 2 ) A thin film comprising a polymer made from ethylene, one or more branched vinyl ester monomers, and optionally vinyl acetate, having a viscosity of 0.1 g / 10 min to 100 g / 10 min.

2. the polymer composition a grafting agent in an amount of 0.01 phr to 1 phr; Adhesion promoter in an amount of 0.01 phr to 15 phr; a first antioxidant in an amount of 0.002 phr to 1 phr; a second antioxidant in an amount of 0.002 phr to 1 phr; an acid scavenger in an amount of 0.002 phr to 1 phr; Light stabilizers in amounts of 0.002 phr to 1 phr; UV absorbers in amounts of 0.002 phr to 1 phr; anti-fog agent in an amount of 0.002 phr to 1 phr; Processing aids in amounts of 0.002 phr to 1 phr; an antiblock agent in an amount of 0.002 phr to 1 phr; or Optionally, at least one additive selected from the group consisting of heat stabilizers, plasticizers, rubbers, elastomers, fillers, antistatic agents, nucleating agents, and combinations thereof.

10. The thin film of claim 1, further comprising one or more of:

3. The one or more branched vinyl ester monomers have the general structure (II): 【Chemical 1】 (In the formula, R 4 and R 5 has a total of 7 carbon atoms) 3. The thin film according to claim 1, wherein

4. 4. The thin film according to any one of claims 1 to 3, wherein the polymer has a total comonomer content in the range of 0.01% to 60% by weight, preferably 5% to 60% by weight, or 5% to 40% by weight.

5. 5. The thin film according to any one of claims 1 to 4, wherein the polymer comprises vinyl ester monomers in an amount ranging from 0.01% to 60% by weight, preferably from 0.1% to 55% by weight or from 5% to 50% by weight.

6. The polymer has a modulus of 0.8 g / cm as measured according to ASTM D792. 3 ~1.3g / cm 3 Density in the range of 0.92 g / cm 3 ~0.96g / cm 3 6. The thin film according to claim 1, having a density in the range of

7. The thin film has the following characteristics: - 22000μm.g / m, measured according to ASTM F1249 2 Water vapor transmission coefficient less than .day; a melting point, measured according to ASTM D3418, of less than 120°C, preferably in the range of 60°C to 100°C; - Haze less than 10% measured according to ASTM D1003; - At least 77% gloss at 45° measured according to ASTM D2457; - at least 90% gloss at 60° measured according to ASTM D2457; and - Glass transition temperature below 0°C via tan δ and glass transition temperature below 0°C via loss modulus, measured by DMA, tensile fixture, tension ° / min according to ASTM D4065 7. The thin film of claim 1, wherein the thin film has one or more of the following:

8. The polymer has a melt index (I) ranging from 0.2 g / 10 min to 100 g / 10 min, as measured according to ASTM D1238 (190°C and 2.16 kg load). 2 ), preferably in the range of 0.2 g / 10 min to 25 g / 10 min. 2 8. The thin film according to claim 1, wherein

9. 9. The thin film according to any one of claims 1 to 8, wherein the thin film has a thickness in the range of 0.5 μm to 1000 μm, or preferably in the range of 10 μm to 600 μm.

10. 10. A method of producing a thin film comprising cast film extrusion, blown film extrusion, calendering, extrusion blow molding, injection molding, injection stretch blow molding, pipe extrusion or thermoforming the thin film of any one of claims 1 to 9.

11. A molded article comprising two substrates and a thin film according to any one of claims 1 to 9 between them.

12. 12. The molded article of claim 11, wherein at least one of the substrates is formed by cast film extrusion, blown film extrusion, extrusion blow molding, injection molding, injection stretch blow molding, pipe extrusion, thermoforming, or calendering.

13. 13. The molded article of claim 11 or 12, wherein the molded article is selected from the group consisting of flexible food packaging, containers, bottles, blow molded tanks, and pipes.

14. 1. A method for producing a molded article, comprising: applying a thin film according to any one of claims 1 to 9 to a substrate; and placing a second substrate on the thin film A method comprising:

15. 15. The method of claim 14, wherein the applying step comprises co-extrusion, extrusion coating, cast film extrusion, blown film extrusion, extrusion blow molding, injection molding, injection stretch blow molding, pipe extrusion, thermoforming, and / or calendering the thin film with a substrate.

Images