# Patent

## Title
Polyolefin adhesive material for use in solar modules

## Abstract

This disclosure generally relates to films capable of use in electronic device modules and to electronic device modules including such films. The disclosure also generally relates to materials for use in such films.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a national stage filing under 35 U.S.C. 371 of International Application No. PCT/US2012/050096, filed Aug. 9, 2012, which claims priority to U.S. Provisional Application No 61/555,912, filed Nov. 4, 2011. The disclosures of both applications are incorporated by reference in their entirety herein.


FIELD OF THE DISCLOSURE
This disclosure generally relates to films capable of use in a photovoltaic solar module, rolls of films capable of use in a photovoltaic solar module, processes of making the films and rolls of films, and to photovoltaic solar modules including such films.
BACKGROUND
Three basic constructions of photovoltaic solar modules are commercially available. The first construction of solar module 10 is shown in FIG. 1 and includes a photovoltaic cell 20 embedded in encapsulant 30. Two panels of glass (or other suitable material) 40, 50 are positioned adjacent to the frontside and backside of the encapsulant. The encapsulant protects the fragile solar cells and adheres them to the frontside and backside glass layers. Typically, this construction of solar module includes encapsulant on both sides of the solar cell. This can be accomplished, for example, by including a frontside layer of encapsulant (positioned to face the sun) and a backside layer of encapsulant (positioned furthest from the sun). Front side encapsulant layers are preferably highly transmissive while backside encapsulant layers need not have the same level of transmissivity. This construction of photovoltaic solar module is generally described in, for example, U.S. Patent Publication No. 2008/0078445.
The second construction of solar module 60 is shown in FIG. 2 and includes a photovoltaic cell 70 positioned between a single encapsulant layer 80 and a backing material 90 (typically glass). Solar panel 60 also includes a protective layer 100 adjacent to encapsulant layer 80. As shown in FIG. 2, this solar panel design includes a frontside encapsulant and no backside encapsulant. This construction of photovoltaic solar module is generally described in, for example. This construction of a photovoltaic solar module is generally described in, for example, U.S. Patent Publication No. 2008/0078445.
The third construction of solar module 110 is shown in FIG. 3 and includes a photovoltaic cell 120 positioned between a single encapsulant layer 130 and a protective layer 150. Solar panel 110 also includes a backing layer 140 (typically glass) adjacent to encapsulant layer 130. As shown in FIG. 3, this solar panel design includes a backside encapsulant and no frontside encapsulant. This construction of photovoltaic solar module is generally described in, for example, U.S. Pat. No. 5,248,349.
SUMMARY
Some exemplary encapsulant layers include ethylene vinyl acetate (EVA) and a cross-linking agent (e.g., peroxide). The inventors of the present disclosure recognized that although crosslinked EVA films often have high strength, they can suffer from a relatively high water vapor transmission rate, yellowing, and possible corrosion due to release of acetic acid.
Solar panel operating temperatures have been measured as high as 110° C. The inventors of the present application recognized that encapsulant films including thermoplastic adhesives can soften at this elevated temperature, causing creep in the panel and possibly resulting in shorting of the photovoltaic cell. These encapsulant films may also be susceptible to UV-induced breakdown, necessitating inclusion of large amounts of UV absorber, which limits the amount of incident light that can be used to power the solar cell. The inventors of the present disclosure also recognized that thermoset adhesives can suffer from slower extrusion processing speeds, causing increased manufacturing cost.
Consequently, there is a need for encapsulant films and materials that minimize the incidence of creep, shrinkage, light transmission, yellowing, corrosion, and delamination while maintaining or improving film processability and manufacturing cost. The inventors of the present disclosure have discovered encapsulant films, materials for use in such films, and solar modules including such films and materials that provide at least one of improved performance, cost, and processability.
In one exemplary embodiment, the present disclosure relates to a film capable of use in a photovoltaic solar module, comprising: a polyolefin; a silane; one or more cross-linking agents; and a plasticizer. The film has an average % transmittance of at least 90% over a wavelength range of 400-1100 nm.
In some embodiments, the plasticizer is non-polar. In some embodiments, the plasticizer is selected from a group consisting essentially of ethylene/α-olefin copolymers and C4-C10 polyolefin homopolymers. In some embodiments, the plasticizer has a Tg<−50° C. In some embodiments, the plasticizer has a Tg<−70° C. In some embodiments, the plasticizer is liquid at 20° C. In some embodiments, the polyolefin is an ethylene/α-olefin copolymer. In some embodiments, the α-olefin moiety of the ethylene/α-olefin copolymer includes four or more carbons. In some embodiments, the ethylene/α-olefin copolymer is a low crystalline ethylene/α-olefin copolymer. In some embodiments, the low crystalline ethylene/α-olefin copolymer has a DSC peak melting point of less than or equal to 50° C. In some embodiments, the low crystalline ethylene/α-olefin copolymer is a butene α-olefin. In some embodiments, the film is greater than 70% by weight of low crystalline ethylene/α-olefin copolymer. In some embodiments, the silane is an unsaturated alkoxysilane. In some embodiments, the unsaturated alkoxysilane is an acrylic alkoxysilane. In some embodiments, the one or more cross-linking agents are one of a thermal curative and a photo-curative. In some embodiments, the thermal curative is a peroxide. In some embodiments, the film further includes a coagent. In some embodiments, the film further includes an additional resin. In some embodiments, the additional resin is an additional low crystalline ethylene/α-olefin copolymer. In some embodiments, the additional resin is one of an ethylene/butene
copolymer and an ethylene/octene copolymer. In some embodiments, the film further includes a hindered amine light stabilizer with a ultraviolet cutoff of 310 nm. In some embodiments, the film further includes an ultraviolet absorber with an ultraviolet cutoff selected from a group consisting essentially of 320, 330, 340, 350, 360, 370, and 380 nm. In some embodiments, the film has an average % transmittance of the film is at least 90% over a wavelength range of 400-1100 nm after exposure to an 85/85 durability test for 1000 hrs. In some embodiments, a machine direction shrinkage measurement of the film is less than a machine direction shrinkage measurement of a film not including plasticizer. In some embodiments, a storage modulii measurement of the film at 100° C. is greater than storage modulii measurement at 100° C. of a film not including the plasticizer. In some embodiments, a storage modulii measurement of the film at 150° C. is greater than storage modulii measurement at 150° C. of a film not including the plasticizer. In some embodiments, a gel fraction of the film is less than 20%. In some embodiments, a gel fraction of the film is less than 5%. In some embodiments, the film includes multiple layers. In some embodiments, the film is in a solar cell module.



BRIEF DESCRIPTION OF THE DRAWINGS
The present disclosure may be more completely understood in consideration of the following detailed description of various embodiments of the disclosure in connection with the accompanying drawings, in which:
FIG. 1 is a cross-sectional view of one type of prior art photovoltaic solar module.
FIG. 2 is a cross-sectional view of one type of prior art photovoltaic solar module.
FIG. 3 is a cross-sectional view of one type of prior art photovoltaic solar module.



The figures are not necessarily to scale. It will be understood that the use of a number to refer to a component in a given figure is not intended to limit the component in another figure labeled with the same number.
DETAILED DESCRIPTION
In the following detailed description, reference may be made to the accompanying set of drawings that form a part hereof and in which are shown by way of illustration several specific embodiments. It is to be understood that other embodiments are contemplated and may be made without departing from the scope or spirit of the present disclosure. The following detailed description, therefore, is not to be taken in a limiting sense.
The present application generally relates to films capable of use in solar modules. The films of the present disclosure can be used in any type of photovoltaic solar module, including, for example, any of the solar modules described in the background. In one exemplary embodiment, a film capable of use in a photovoltaic solar module includes a polyolefin, a silane, one or more cross-linking agents, and a plasticizer. The film has an average % transmittance of at least 90% over a wavelength range of 400-1100 nm. Each of the components of the film will be discussed in greater detail below.
Polyolefin
In some embodiments, the polyolefin is one or more of EVA, high density polyethylene, ionomers, polystyrene, and poly vinyl butarate.
In some embodiments, the polyolefin is an ethylene/α-olefin copolymer. As used herein, the term “ethylene/α-olefin copolymer” refers to polymers comprising a class of hydrocarbons manufactured by the catalytic oligomerization (i.e., polymerization to low-molecular-weight products) of ethylene and linear α-olefin monomers. The ethylene/α-olefin copolymers may be made, for example, with a single site catalyst such as a metallocene catalyst or multi-site catalysts such as Ziegler-Natta and Phillips catalysts. The linear α-olefin monomers typically are 1-butene or 1-octene but may range from C3 to C20 linear, branched or cyclic α-olefin. The α-olefin may be branched but only if the branch is at least alpha to the double bond, such as 3-methyl-1-pentene. Examples of C3-C20 α-olefins include propylene, 1-butene, 4-methyl-1-butene, 1-hexene, 1-octene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. The α-olefins can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-1 propene (allyl cyclohexane) and vinyl cyclohexane. Although not α-olefins in the classical sense of the term, for purposes of this disclosure certain cyclic olefins, such as norbornene and related olefins, are α-olefins and can be used. Similarly, styrene and its related olefins (for example, α-methyl styrene) are α-olefins for the purposes of this disclosure. Acrylic and methacrylic acid and their respective ionomers, and acrylates and methacrylates, however are not α-olefins for the purposes of this disclosure. Illustrative ethylene/α-olefin copolymers include ethylene/1-butene, ethylene/1-octene, ethylene/1-butene/1-octene, ethylene/styrene. The polymers can be block or random. Exemplary commercially available low crystalline ethylene/α-olefin copolymers include resins sold under the tradenames “ENGAGE” ethylene/1-butene and ethylene/1-octene copolymers and “FLEXOMER” ethylene/1-hexene copolymer, available from Dow Chemical Co., and homogeneously branched, substantially linear ethylene/α-olefin copolymers such as “TAFMER”, available from Mitsui Petrochemicals Company Limited, and “EXACT”, available from ExxonMobil Corp. As used herein, the term “copolymer” refers to polymers made from at least 2 monomers.
In some of these embodiments, the α-olefin moiety of the ethylene/α-olefin copolymer includes four or more carbons. In some embodiments, the ethylene/α-olefin copolymer is a low crystalline ethylene/α-olefin copolymer. As used herein, the term “low crystalline” means crystallinity (according to method disclosed in ASTM F2625-07) of less than 50% by weight. In some embodiments, the low crystalline ethylene/α-olefin copolymer is a butene α-olefin. In some embodiments the α-olefin of the low crystalline ethylene/α-olefin copolymer has 4 or more carbons.
In some embodiments, the low crystalline ethylene/α-olefin copolymer has a DSC peak melting point of less than or equal to 50° C. As used herein, the term “DSC peak melting point” means a melting point determined by DSC (10°/min) under nitrogen purge as the peak with the largest area under the DSC curve.
In some embodiments, the film is greater than 35% by weight low crystalline ethylene/α-olefin copolymer. In some embodiments, the film is greater than 50% by weight low crystalline ethylene/α-olefin copolymer. In some embodiments, the film is greater than 70% by weight low crystalline ethylene/α-olefin copolymer.
In some embodiments, the film includes additional polyolefin resins. Exemplary additional resins include, for example, low crystalline ethylene/α-olefin copolymer, HDPE, and polystyrene. In embodiments where the additional resin is a low crystalline ethylene/α-olefin copolymer, the two copolymers could, for example, have respective DSC peak melting points of, for example, less than 50° C. and greater than 50° C. In alternative exemplary embodiments, one low crystalline ethylene/α-olefin copolymer could have a DSC peak melting point of less than 50° C. while the other low crystalline ethylene/α-olefin copolymer could have a DSC peak melting point of greater than 55° C., or greater than 60° C., or greater than 65° C., or greater than 70° C., or greater than 75° C. In another exemplary embodiment one low crystalline ethylene/α-olefin copolymer could have a DSC peak melting point of greater than 50° C. while the other low crystalline ethylene/α-olefin copolymer could have a DSC peak melting point of less than 45° C., or less than 40° C., or less than 35° C. In an alternative exemplary embodiment, one of the two low crystalline ethylene/α-olefin copolymers is ethylene/butene copolymer and the other is an ethylene/octene copolymer.
Silane
Exemplary silanes for use in the films of the present disclosure include, for example, silanes that include an ethylenically unsaturated hydrocarbyl group (such as, for example, vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or γ-(meth)acryloxy allyl group) and a hydrolysable group (such as, for example, methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, alkyl, arylamino, hydrocarbonyloxy or hydrocarbylamino groups). In some exemplary embodiments, the silane is an unsaturated alkoxysilane. In some exemplary embodiments, the unsaturated alkoxysilane is an acrylic silane. Some examples include vinyl trimethoxysilane, vinyl triethoxysilane, and 3-(meth)acryloxypropyl trimethoxysilane. Commercially available examples include “SILQUEST A174 and SILQUEST A171”.
The amount of silane is typically at least about 0.05%, for example 0.1%, for example 0.5%, for example 1.0%, for example 2.0%, for example 10.0%, or even for example 10.0%.
Cross-Linking Agents
The films of the present disclosure include one or more cross-linking agents. Exemplary cross-linking agents include, for example, thermal and photo cross-linking agents. Some exemplary thermal cross-linking agents include, for example, peroxides. Some exemplary peroxides include, for example, diacyl peroxides (such as, for example, dilauryl peroxide and didecanoyl peroxide), alkyl peresters (such as, for example, tert-butyl peroxy-2-ethylhexanoate), perketals (such as, for example, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane or 1,1-di(tert-butylperoxy)cyclohexane), dialkyl peroxides (such as, for example, tert-butyl cumyl peroxide, di(tert-butyl)peroxide and dicumyl peroxide), C-radical donors (such as, for example, 3,4-dimethyl-3,4-diphenylhexane and 2,3-dimethyl-2,3-diphenylbutane), and azo compounds (such as, for example, 2,2′-azodi (2-acetoxypropane)). Additional exemplary azo compounds include those described in U.S. Pat. Nos. 3,862,107 and 4,129,531. Some exemplary commercially available peroxides include, for example, “LUPEROX TBEC”, “LUPEROX 231”, and “LUPEROX P. Mixtures of two or more cross-linking agents may be used.
The amount of cross-linking agent varies, but the minimum amount is that sufficient to afford the desired range of crosslinking. In some embodiments, the film includes at least about 0.05%. In some embodiments, the film includes at least about 0.5%. In some embodiments, the film includes at least about 1.0%. In some embodiments, the film includes at least about 2.0%. In some embodiments, the film includes at least about 5.0%.
Plasticizer(s)
Preferred plasticizers for use in the films described herein are those that are non fugitive and/or crosslink the polymers in the film. Plasticizers used in the films described herein may improve extrusion processing speed and reduce film shrinkage while increasing storage modulus (creep resistance) at temperatures between about 100° C. and 200° C. Preferably, such plasticizers also are not substantially tacky at normal handling or storage temperatures. In some exemplary embodiments, the plasticizer(s) used in the films are liquids at 20° C. In some exemplary embodiments, the plasticizer does not act as a tackifier.
In some exemplary embodiments, the plasticizer is non-polar. As used herein, the term “nonpolar plasticizer” means a nonpolar additive that increases the plasticity, fluidity or flowability of a low crystalline ethylene/α-olefin polymer and has a MW of less than 10,000 as determined by ASTM D6474. As used herein, nonpolar plasticizers do not include, for example, common polar polyvinylchloride (PVC) plasticizers such as phthalic acid diesters (e.g., diethylphthlate, dibutylphthlate, dioctylphthlate) or other polar ester plasticizers such as trimellitates, adipates, sebacates, maleates, citrates or benzoates. Examples of non-polar plasticizers include, for example, ethylene/α-olefin copolymers and C4-C10 polyolefin homopolymers. In some exemplary embodiments, the nonpolar plasticizer may be selected from the group consisting of ethylene/α-olefin copolymers and C4-C10 polyolefin homopolymers.
Exemplary commercially available nonpolar plasticizers include those under the tradename “SPECTRASYN” commercially available from ExxonMobil Chemical, Baton Rouge, La., “KAYDOL” white mineral oil commercially available from Sonneborn Refined Products B.V., Amsterdam, the Netherlands, “INDOPOL” polybutenes commercially available from Ineos Oligomers, League City, Tex. and “TRILENE” ethylene propylene (EP) or EPDM copolymers commercially available from Lion Copolymer, Baton Rouge, La.
The nonpolar plasticizer may have a Tg of less than −50° C., for example less than −55° C., for example less than −65° C., for example less than −70° C., or even for example less than −75° C. The plasticizer may have a DSC peak melting point of less than 80° C., for example less than 60° C., for example less than 40° C. or even for example less than 20° C. In one embodiment the plasticizer is a liquid at 20° C.
In some exemplary embodiments, conventional plasticizers such as are commonly used for poly(vinyl chloride) are substantially absent. As used in this paragraph, the term “substantially absent,” means that these compounds are not added deliberately to the compositions and—if present—comprise less than 0.5 wt % of the total film composition.
In particular, plasticizers such as phthalates, adipates, trimellitate esters, polyesters, and other functionalized plasticizers as disclosed in, for example, U.S. Pat. Nos. 3,318,835; 4,409,345; WO 02/31044 A1; and PLASTICS ADDITIVES 499-504 (Geolfirey Pritchard, ed., Chapman & Hall 1998) are substantially absent.
The amount of plasticizer is typically at least about 0.5%. In some embodiments, the amount of plasticizer is at least about 1.0%. In some embodiments, the amount of plasticizer is at least about 2.0%. In some embodiments, the amount of plasticizer is at least about 5.0%. In some embodiments, the amount of plasticizer is at least about 10.0%. In some embodiments, the amount of plasticizer is at least about 20.0%.
Additives
In some exemplary embodiments, the films of the present disclosure include a coagent. Exemplary coagents include, for example, free radical crosslinking coagents (promoters or co-initiators). Examples of such coagents include multifunctional vinyl monomers and polymers, triallyl isocyanuarate, trimethylolpropane trimethylacrylate, divinyl benzene, acrylates and methacrylates of polyols, allyl alcohol derivatives, and low molecular weight polybutadiene. Sulfur crosslinking promoters include benzothiazyl disulfide, 2-mercaptobenothiazole and tetramethylthiuram tetrasulfide.
In some exemplary embodiments, the film further includes one or more UV absorbers. UV absorbers absorb light and can thereby protect polymeric materials and/or solar cells. Some exemplary UV absorbers include, for example, triazines, benzotriazoles, hydroxybenzophenones, hydroxyphenyltriazines, esters of benzoic acids, and mixtures of two or more thereof. In some exemplary embodiments, the films of the present disclosure include 0.01% UV absorber. In some exemplary embodiments, the films of the present disclosure include 0.1% UV absorber. In some exemplary embodiments, the films of the present disclosure include 0.5% UV absorber. In some exemplary embodiments, the films of the present disclosure include 1% UV absorber.
Films including UV absorbers have “UV cutoffs.” As used herein, the term “UV cutoff” refers to the wavelength transmission of a film and means that the film will block substantially all UV light below the specified wavelength threshold. In some embodiments, the films of the present disclosure have a “UV cutoff” of 310, 350, and 380 nm, respectively. Such films can, for example, include less than 0.5% of “TINUVIN 622” HALS, “CHIMASSORB 81” UV absorber, or “TINUVIN 460” UV absorber, respectively.
In some exemplary embodiments, the film includes one or more hindered amine light stabilizer (“HALS”). HALS are light stabilizers rather than absorbers and scavenges radicals by production of nitroxyl radicals. In some embodiments, inclusion of a HALS instead of a UV absorber may permit entry of more light energy into a solar cell. Some exemplary HALS include, for example, cyclic amines, secondary, tertiary, acetylated, N-hydrocarbyloxy substituted, hydroxy substituted N-hydrocarbyloxy substituted, or other substituted cyclic amines which are further characterized by a degree of steric hindrance, generally as a result of substitution of an aliphatic group or groups on the carbon atoms adjacent to the amine function.
In some exemplary embodiments, the films of the present disclosure include 0.01% HALS. In some exemplary embodiments, the films of the present disclosure include 0.1% HALS. In some exemplary embodiments, the films of the present disclosure include 0.5% HALS. In some exemplary embodiments, the films of the present disclosure include 1% HALS.
Other additives include, for example, pigments such as carbon black and titanium dioxide; inorganic fillers such as talc, fumed silica, precipitated silica, barium sulfate and calcium carbonate; crosslinkers; anti-oxidants; scorch inhibitors; flame retardants; and catalysts for crosslinking such as organo tin compounds, for example di-n-butyl tin dilaurate. Other suitable catalysts include, for example titanium compounds and metal alkoxides, for example aluminum isopropoxide and zirconium isopropoxide.
The films of the present disclosure can be manufactured using known techniques in the art of film forming, including coating and curing on a release liner and extrusion coating. In some embodiments, the films can be used as an adhesive and may be exposed to further processing, e.g., heat and pressure. In some embodiments, the films are extruded. In some exemplary embodiments, the films of the present disclosure are delivered in film form. In some exemplary embodiments, the films of the present disclosure include a standard matte finish. In some exemplary embodiments, the films of the present disclosure are provided on a release liner.
In some embodiments, the films include multiple layers. In one exemplary implementation, a film of the present disclosure includes three or more layers. In one exemplary implementation of this, the cross-linking agent(s), silane, and/or polyolefin are in different layers. For example, the cross-linking agent(s) could be substantially or entirely in a center layer and the polyolefin and silane could be in the outer layers. In some embodiments, the films of the present disclosure can be used as a flexible polyolefin backsheet and/or frontsheet.
The films of the present disclosure may be used in a solar module. The solar module may be of any type known in the art. In some embodiments, the films or compositions described herein can be used as an adhesive for a solar module. In such uses, the films or compositions may be referred to as an “assembly adhesive,” since they are used to assemble and hold together at least two elements of the solar module.
In some exemplary embodiments, for example, those where the film is laminated onto a solar cell, a low gel content may be preferred because a film with low gel content provides better adhesion and flexibility until cured at higher temperature to a higher gel content. In some exemplary embodiments, the gel fraction of the uncured film is less than 20% as measured by ASTM D2765-11. In some exemplary embodiments, the gel fraction of the uncured film is less than 10% as measured by ASTM D2765-11. In some exemplary embodiments, the gel fraction of the uncured film is less than 5% as measured by ASTM D2765-11. In some exemplary embodiments, the gel content after cross-linking is at least 40% when measured according to ASTM D2765-11. In some exemplary embodiments, the gel content after cross-linking is at least 50% when measured according to ASTM D2765-11. In some exemplary embodiments, the gel content after cross-linking is at least 60% when measured according to ASTM D2765-11. In some exemplary embodiments, the gel content after cross-linking is at least 70% when measured according to ASTM D2765-11.
The films of the present disclosure have an average % transmittance of at least 90% over a wavelength range of 400-1100 nm. This permits use of the films and compositions of the present disclosure as frontside encapsulant films. In some embodiments, the films of the present disclosure have an average % transmittance of the film is at least 90% over a wavelength range of 400-1100 nm after exposure to an 85/85 durability test for 1000 hrs. In some embodiments, a machine direction shrinkage measurement of the film is less than a machine direction shrinkage measurement of a film not including plasticizer. In some embodiments, a storage modulii measurement of the film at 100° C. is greater than storage modulii measurement at 100° C. of a film not including the plasticizer. In some embodiments, a storage modulii measurement of the film at 150° C. is greater than storage modulii measurement at 150° C. of a film not including the plasticizer.
The encapsulant films and materials of the present disclosure perform at least some of the following advantages over currently available encapsulant films: minimization of the incidence of creep, shrinkage, yellowing, corrosion, and delamination while maintaining or improving light transmission, film processability, and manufacturing cost. Additional advantages and embodiments of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure. In these examples, all percentages, proportions and ratios are by weight unless otherwise indicated.
EXAMPLES
Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, and all reagents used in the examples were obtained, or are available, from general chemical suppliers such as, for example, Sigma-Aldrich Company, Saint Louis, Mo., or may be synthesized by conventional methods.
These following abbreviations are used in the examples:
DSC=differential scanning calorimeter
pph=parts per hundred
% T=Percent transmission,
MW=molecular weight
Mn=number average molecular weight










MATERIALS TABLE
















“EXACT 9361”
A low crystalline ethylene/butene copolymer with



a DSC peak melting point of 41° C., commercially



available from ExxonMobil Chemical, Baton



Rouge, LA


“EXACT 8230”
A low crystalline ethylene/octene copolymer with



a DSC peak melting point of 72° C., commercially



available from ExxonMobil Chemical, Baton



Rouge, LA


“TAFMER DF740”
A low crystalline ethylene/α-olefin copolymer



with a DSC peak melting point of 55° C.,



commercially available from Mitsui Chemicals,



Tokyo, Japan


“ENGAGE 8200”
A low crystalline ethylene/α-olefin copolymer



with a DSC peak melting point of 59° C.,



commercially available from Dow Chemical



Company, Midland, MI


“ENGAGE 8130”
A low crystalline ethylene/α-olefin copolymer



with a DSC peak melting point of 50° C.,



commercially available from Dow Chemical



Company, Midland, MI


“LUPEROX TBEC”
OO-t-Butyl-O-(2-ethylhexyl)



monoperoxycarbonate peroxide thermal initiator



commercially available from Arkema Inc, King



of Prussia, PA


“SILQUEST A174”
3-Methacryloxypropyl trimethoxysilane



commercially available from Momentive



Performance Materials, Columbus, OH


“TAICROS”
Triallylisocyanurate coagent commercially



available from Evonik Industries AG, Essen,



Germany


“CHIMASSORB 81”
Light stabilizer of 2-hydroxybenzophenone class



commercially available from Ciba Specialty



Chemicals Inc., Basel, Switzerland


“SPECTRASYN 6”
A polyolefin homopolymer with a Tg of −91 C.



that is liquid at 20° C. and has a MW of about 450-3000,



commercially available from ExxonMobil



Chemical, Baton Rouge, LA


“AFFINITY GA 1900”
Low MW, low crystalline polyethylene/octene



copolymer having a DSC melting peak at



10° C./min of 68° C., a melt flow index of 2.16 @



190° C. (tested under ASTM D1238) is about



1000, and a Tg of −58° C., commercially available



from Dow Chemical, Midland, MI


“INDOPOL H-50”
A polybutene (isobutylene/butene copolymer)



with a Mn of 800, a bromine number of 20, and



olefinic end groups, commercially available from



Ineos Oligomers, League City, TX


“GLISSOPOL 1000”
A low MW viscous liquid polyisobutene with a



Mn of 1000, a high proportion of terminal double



bonds, an 85-88% α-olefin content, and a Tg of −85° C.,



commercially available from BASF



Corporation, Ludwigshafen, Germany





The melting peaks listed above are either publicly available or were measured using a differential scanning calorimeter (“Q 2000,” sold by TA Instruments, New Castle, Deleware).






Comparative Examples 1-3 (CE1-CE3) and Examples 1A-3A and 1B-3B
The ingredients listed in Table 1 were pre-mixed. The mixtures were then left in a 40° C. environment for 24 hours. Pellets were formed. These pellets were fed into a 31.75 mm diameter single screw extruder (sold by Killion Cedar Grove, N.J.) having a length of 762 mm. The single screw extruder included a barrier screw with a Maddock mixer in the last section. The extruder temperature control unit was divided into three barrel sections plus outlet adapters. The temperature profile of the three barrel sections was 121° C., 110° C., and 110° C., and the outlet adapters were maintained at 110° C. A 152 mm wide coat hanger type extrusion die (sold by Brabenderm, Duisburg, Germany) was attached at the outlet of the extruder. The die was used to form the polymer into a film. The gap of the die was measured during operation with feeler gauges to determine the gap to be between 0.95 mm and 1 mm. The temperature of the die was 121° C. Extrudate from the film was taken away by a 11.6 micron Ra surface roughness cast roll 305 mm in diameter, moving with a surface velocity of 1.4 m/min. The die outlet was positioned at the 9:00 position as compared to the cast roll, 12 mm distance from the roll. The polymer film was drawn over the top of the roll by the motion of the cast roll. The contact point of the polymer film onto the roll was therefore above the outlet of the die. The contact point of the film on the roll was 60 mm from the outlet of the die. The temperature of the roll was 21° C. The film followed the cast roll until the 2:00 position and was subsequently hand rolled onto a fiberboard core.
Comparative Examples 4A, 4B, 5 (CE4A, CE4B, CE5) and Examples 4, 5, and 6
The ingredients listed in Table 1 were pre-mixed. The mixtures were then left in a 40° C. environment for 24 hours. This mixture was then processed in an extruder (Model EPL V5502 sold by C.W. Brabender Instruments, Inc.) for 5 min at 90° C. and pressed to an 18 mil thickness using a Carver Hydraulic press (model 3925).
The following was the lamination procedure used. Both sides of a 6 inch×6 inch square of float glass was cleaned with isopropanol and dried. The square float of glass had a tin side (having a hazy blue glow under UV light) and a non-tin side. A 6 square inch by 18 mil thick film sample was cut from the samples formed as described above. A 0.75 inch×6 inch piece of release liner (a 2 mil polyester release liner from Mitsubishi) was placed between the glass and the film sample on one edge to aid as a “starter” tab to grab on to. A 6 inch×6 inch piece of solar backsheet (commercially available under the trade designation “3M SCOTCHSHIELD 17” from 3M, St. Paul, Minn.) was cut and placed with the smooth EVA side on the film sample. The construction was then laminated at 150° C. for 15 min in a Photovoltaic Module Laminator LM-50×50-S sold by NPC Group.







TABLE 1







Formulations























CE1
EX1A
EX1B
CE2
EX2A
EX2B
CE3
EX3A
EX3B
CE4A
CE4B
EX4
CE5
EX5
EX6


























“EXACT 9361”
100
100
100
0
0
0
0
0
0
24
24
24
0
0
24


“ENGAGE 8200”
0
0
0
100
100
100
0
0
0
0
0
0
0
0
0


“ENGAGE 8130”
0
0
0
0
0
0
0
0
0
0
0
0
100
100
0


“TAFMER DF740”
0
0
0
0
0
0
100
100
100
0
0
0
0
0
0


“EXACT 8230”
0
0
0
0
0
0
0
0
0
72
72
72
0
0
72


“SPECTRASYN 6”
0
2
5
0
2
5
0
2
5
0
0
2
0
2
0


“LUPEROX TBEC”
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1


“SILQUEST A174”
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8


“TAICROS”
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8


“CHIMASSORB 81”
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


“AFFINITY GA
0
0
0
0
0
0
0
0
0
4
4
4
0
0
4


1900”


“INDOPOL H-50”
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2


“GLISSOPOL 1000”
0
0
0
0
0
0
0
0
0
0
2
0
0
0
0





NOTE:


Total copolymer(s) add to 100 and all other ingredients are based on part per hundred (pph) copolymer






Example 4 was subjected to the following durability testing: Samples were placed in a preheated and prehumidifed “CASCADE SE-1000-6-6” environmental chamber (commercially available from Thermotron, Holland, Mich.) and taken out at after the stated number of hours. This test can be referred to as an “85/85 Durability Test.” The results of this test for Example 4 were as follows: 120 N/cm adhesion initially and 85 N/cm after 250 hrs (standard deviations of 20 for adhesion).
An 18 mil thick sample of Example 4 that had been run through the above-described 85/85 durability test was placed between a 1 inch×1 inch piece of boro float glass and was then laminated at 150° C. for 15 min. The sample was then placed in the chamber (“SUNARAY 400 SM UV FLOOD CURING SYSTEM” 00000446 commercially available from Uvitron International, West Springfield, Mass.) with a radiation flux of 72 W (315-400 nm) with a 400 W metal halide UV source for the time stated. This test can be referred to as a “UV Durability Test.” The results of this test for Example 4 were as follows: 91% transmission initially and 91% transmission after 2000 hours.
Shrinkage was measured as follows. An 18 mil thick film was marked with three lines each measuring 3×6 inch in length and placed in an oven at 150° C. for 10 min on a talc bed. The sample was removed and cooled, and the average length change of the three lines was calculated. The % change was calculated and is reported as % shrinkage.
Storage Modulus was measured as follows. A dynamic mechanical analyzer (“Q 800,” sold by TA Instruments, New Castle, Deleware) was used to characterize storage modulus from −90° C. to 200° C. at 3° C./min at 1 Hz frequency in tensile mode. The sample dimensions were 10 mm×6 mm×18 mil.







TABLE 2







Shrinkage and Storage Modulus












Storage Modulus
Storage Modulus


Example
% Shrinkage1
kPa (100° C.)
kPa (150° C.)





CE1
34
626
457


EX1B
29
697
526


EX1C
25
N/A
N/A


CE2
35
N/A
N/A


EX2A
29
N/A
N/A


EX2B
21
N/A
N/A


CE3
51
N/A
N/A


EX3A
42
N/A
N/A


EX3B
34
N/A
N/A


CE4A
N/A
309
142


CE4B
N/A
244
 66


EX4
N/A
385
220


CE5
N/A
354
244


EX 5
N/A
471
351


EX6
N/A
323
175





1= shrinkage is average of three measurements with standard deviations of 1-2%


N/A means not measured






Adhesion

An unaged, laminated sample as described above was placed in a preheated and prehumidifed “CASCADE SE-1000-6-6” environmental chamber (commercially available from Thermotron, Holland, Mich.) and taken out after 120 hours. The samples were then cut into half inch wide strips. A 90 degree peel test was then performed, according to ASTM D6862-04, at a pulling rate of 6 inch per minute using an “MTS INSIGHT,” 101N extended length model, commercially available from MTS Systems Corporation, Eden Prarie, Minn. Replicates were performed and an average adhesion value was calculated. The adhesion of Example 4 was determined to be 128N/cm.
Light Transmission
A sample measuring 1.8 inch×1.8 inch×18 mil was positioned between two 2 inch×2 inch boro float glass pieces (tin side facing away from samples) and laminated using at 150° C. for 15 min in a “SPI-LAMINATOR 350 DCN 299” laminator commercially available from Spire Corporation, Bedford, Mass. Light transmission was determined by measuring the average transmission between 400 nm and 1100 nm using a Lambda 900 spectrophotometer (sold by TDK-Lambda Americas Inc.). The percent light transmission of Example 4 was determined to be 91.1 initially after lamination and 90.8 (with a standard deviation of +/−0.1) after 1000 hours exposure under the 85/85 durability test described above.
As used herein, the terms “a”, “an”, and “the” are used interchangeably and mean one or more; “and/or” is used to indicate one or both stated cases may occur, for example A and/or B includes, (A and B) and (A or B).
All references mentioned herein are incorporated by reference.
Unless otherwise indicated, all numbers expressing feature sizes, amounts, and physical properties used in the present disclosure and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings disclosed herein.
As used in this specification and the appended claims, the singular forms “a”, “an”, and “the” encompass embodiments having plural referents, unless the content clearly dictates otherwise. As used in this disclosure and the appended claims, the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
Various embodiments and implementation of the present disclosure are disclosed. The disclosed embodiments are presented for purposes of illustration and not limitation. The implementations described above and other implementations are within the scope of the following claims. One skilled in the art will appreciate that the present disclosure can be practiced with embodiments and implementations other than those disclosed. Those having skill in the art will appreciate that many changes may be made to the details of the above-described embodiments and implementations without departing from the underlying principles thereof. It should be understood that this disclosure is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the disclosure intended to be limited only by the claims set forth herein as follows. Further, various modifications and alterations of the present disclosure will become apparent to those skilled in the art without departing from the spirit and scope of the present disclosure. The scope of the present application should, therefore, be determined only by the following claims.

## Claims

1. A film capable of use in a photovoltaic solar module, comprising:
a polyolefin;
a silane;
one or more cross-linking agents; and
a plasticizer;
wherein the average % transmittance of the film is at least 90% over a wavelength range of 400-1100 nm, and
wherein the plasticizer comprises a C4-C10 polyolefin homopolymer.

2. The film of claim 1, wherein the plasticizer has a Tg<−50° C.

3. The film of claim 1, wherein the polyolefin is an ethylene/α-olefin copolymer.

4. The film of claim 1, wherein the ethylene/α-olefin copolymer is a low crystalline ethylene/α-olefin copolymer.

5. The film of claim 4, wherein the low crystalline ethylene/α-olefin copolymer has a DSC peak melting point of less than or equal to 50° C.

6. The film of claim 4, wherein the low crystalline ethylene/α-olefin copolymer is a butene α-olefin.

7. The film of claim 1, wherein the silane is an unsaturated alkoxysilane.

8. The film of claim 1, wherein the unsaturated alkoxysilane is an acrylic alkoxysilane.

9. The film of claim 1, wherein the one or more cross-linking agents are one of a thermal curative and a photo-curative.

10. The film of claim 9, wherein the thermal curative is a peroxide.

11. The film of claim 1, further comprising an additional resin.

12. The film of claim 11, wherein the additional resin is an additional low crystalline ethylene/α-olefin copolymer.

13. The film of claim 1, further comprising an ultraviolet absorber with a ultraviolet cutoff selected from a group consisting essentially of 320, 330, 340, 350, 360, 370, and 380 nm.

14. The film of claim 1, wherein the average % transmittance of the film is at least 90% over a wavelength range of 400-1100 nm after exposure to an 85/85 durability test for 1000 hrs.

15. The film of claim 1, wherein a machine direction shrinkage measurement of the film is less than a machine direction shrinkage measurement of a film not including plasticizer.

16. The film of claim 1, wherein a storage modulii measurement of the film at 100° C. is greater than storage modulii measurement at 100° C. of a film not including the plasticizer.

17. The film of claim 1, wherein a storage modulii measurement of the film at 150° C. is greater than storage modulii measurement at 150° C. of a film not including the plasticizer.

18. The film of claim 1, wherein a gel fraction of the film is less than 5%.

19. The film of claim 1, in a solar cell module.