Compositions and articles comprising (METH)acrylate polymer and monomer

Abstract

Compositions and articles are described comprising a (e.g. cured) composition bonded to a substrate. The composition comprises a) at least 15 wt.% of polymerized units of polymer(s) having a weight average molecular weight of 10,000 to 100,000 g / mole and at least two (meth)acrylate groups. The polymer typically has a low Tg. The composition further comprises b) at least 15 wt.% of a polymerized units of (meth)acrylate monomer(s); and / or c) 10 to 40 wt.% of polymerized units of ethylenically unsaturated monomer(s) comprising a moiety selected from acidic moieties, amide moieties, or a combination thereof.

Description

[0001] COMPOSITIONS AND ARTICLES COMPRISING (METH)ACRYLATE POLYMER AND MONOMER Summary In one embodiment, an article is described comprising a (e.g. cured) composition bonded to a substrate. The composition comprises a) at least 15 wt.% of polymerized units of polymer(s) having a weight average molecular weight of 10,000 to 100,000 g / mole and at least two (meth)acrylate groups; b) at least 15 wt.% of a polymerized units of (meth)acrylate monomer(s); c) 10 to 40 wt.% of polymerized units of ethylenically unsaturated monomer(s) comprising a moiety selected from acidic moieties, amide moieties, or a combination thereof. In another embodiment, compositions comprising a) at least 15 wt.% of a polymer(s) having a weight average molecular weight of 10,000 to 100,000 g / mole and at least two (meth)acrylate groups; b) at least 15 wt.% of (meth)acrylate monomer(s); c) 10 to 40 wt.% of ethylenically unsaturated monomer(s) comprising a moiety selected from acidic moieties, amide moieties, or a combination thereof. The polymer typically has a Tg less than 0°C or -25°C. The polymer typically has a molecular weight of at least 15,000; 20,000; 25,000; 30,000; 35,000, 40,000; 45,000, or 50,000 g / mole. The composition comprises at least 20, 25, 30, 35, 40, 45, 50, 55, 60 wt.% of polymerized units of the polymer. The polymer typically comprises a backbone selected from polyether, polyester, polybutadiene, polycarbonate, or polycaprolactone and optionally urethane moieties. In some embodiments, b) comprises at least one (meth)acrylate monomer wherein a homopolymer thereof has a Tg less than 0°C or -25°C. The composition may comprise less than 40, 35, 30, 25, 20, or 15 wt.% of polymerized units of (meth)acrylate monomer wherein a homopolymer thereof has a Tg less than 0°C or -25°C. The cured composition may be characterized by one or more of the following properties: has one or more of the following properties: a peak tan delta less than 25 or -0°C; an elastic modulus (E’) at 0°C of less than 200, 250, 150, 100, 50, or 25 MPa; an elastic modulus (E’) at -20°C of less than 1500, 1000, 500, 250 or 100 MPa; an elastic modulus (E’) at 25°C of greater than 0.3, 1, or 10 MPa. In some embodiments, the composition is at least a semi-structural adhesive. Written Description Polymer Comprising (Meth)acrylate Groups Presently described are compositions comprising polymer(s) having a weight average molecular weight (Mw) of at least 10,000 g / mole and typically no greater than 100,000 g / mole. In some embodiments, the molecular weight is at least 15,000; 20,000; 25,000, 30,000, 35,000; 40,000, 45,000 or 50,000 g / mole. In some embodiments, the molecular weight no greater than 90,000; 80,000; 70,000, or 60,000 g / mole. In some embodiments, polymers in this molecular weight range are described as oligomers. In typical embodiments, the polydispersity of the polymer is no greater than 3.5, 3.0, 2.5 or 2.0. The composition may comprise a single polymer or two or more polymers within such weight average molecular weight ranges. The molecular weight can be determined by Gel Permeation Chromatograpy, ASTM D6579-11 using polystyrene molecular weight standards and differential refractive index (dRI) detection. A suitable solvent, such as tetrahydrofuran (stabilized with 250 ppm BHT), can be used as the solvent and eluent. The polymer is typically a di(meth)acrylate, having two terminal (meth)acrylate groups. The polymer may be represented by the following formula: H2C=CR1C(O)O-L-Polymer Backbone-L-O(O)CR1=CH2The polymer backbone is typically covalently bonded to terminal (meth)acrylate groups (i.e. R1is hydrogen or methyl) with a linking group, L. The polymer backbone is typically prepared from one or more polyols. Although (e.g. small concentrations of) polyol having greater than two hydroxyl group can be utilized, the polyol is typically predominantly a diol. In some embodiments, the polyol may be at least one of a polyester polyol, a polyether polyol, a polycarbonate polyol, polycaprolactone, and a hydroxyl terminated polybutadiene. Combinations of different types of polyols may be used. In some embodiments, the polymer backbone is a polyester polyol. The polyester polyol may be a product of a polycondensation reaction. When the polyester polyol is prepared with a condensation reaction, the reaction can be between one or more carboxylic acids and one or more diols. Example of carboxylic acids includes carboxylic acid according to Formula III, having the structure: In Formula III, R3 may be chosen from substituted or unsubstituted C1-C40 alkylene, C2-C40 alkylene, C2-C40 alkenylene, C4-C20 arylene, C4-C20 cycloalkylene and C4-C20 aralkylene. Specific examples of suitable carboxylic acids include, but are not limited to, glycolic acid (2-hydroxyethanoic acid), lactic acid (2-hydroxypropanoic acid), succinic acid (butanedioic acid), 3-hydoxybutanoic acid, 3- hydroxypentanoic acid, terephthalic acid (benzene-1,4-dicarboxylic acid), naphthalene dicarboxylic acid, 4-hydroxybenzoic acid, 6-hydroxynaphtalane-2-carboxylic acid, oxalic acid, malonic acid (propanedioic acid), adipic acid (hexanedioic acid), pimelic acid (heptanedioic acid), ethonic acid, suberic acid (octanedioic acid), azelaic acid (nonanedioic acid), sebacic acid (decanedioic acid), glutaric acid (pentanedioic acid), dedecandioic acid, brassylic acid, thapsic acid, maleic acid ((2Z)-but-2-enedioic acid), fumaric acid ((2E)-but-2-enedioic acid), glutaconic acid (pent-2-enedioic acid), 2-decenedioic acid, traumatic acid ((2E)-dodec-2-enedioic acid), muconic acid ((2E,4E)-hexa-2,4-dienedioic acid), glutinic acid, citraconic acid((2Z)-2-methylbut-2-enedioic acid), mesaconic acid ((2E)-2-methyl-2-butenedioic acid), itaconic acid (2-methylidenebutanedioic acid), malic acid (2-hydroxybutanedioic acid), aspartic acid (2-aminobutanedioic acid), glutamic acid (2-aminopentanedioic acid), tartonic acid, tartaric acid (2,3-dihydroxybutanedioic acid), diaminopimelic acid ((2R,6S)-2,6-diaminoheptanedioic acid), saccharic acid ((2S,3S,4S,5R)-2,3,4,5-tetrahydroxyhexanedioic acid), mesooxalic acid, oxaloacetic acid (oxobutanedioic acid), acetonedicarboxylic acid (3-oxopentanedioic acid), arbinaric acid, phthalic acid (benzene-1,2-dicarboxylic acid), isophthalic acid, diphenic acid, 2,6-naphtalenedicarboxylic acid, or a mixture thereof. An example of a suitable diol for the condensation reaction includes a diol according to Formula IV, having the structure: Formula IV. In Formula IV, R4 may be chosen from substituted or unsubstituted C1-C40 alkylene, C2-C40 alkenylene, C4-C20 arylene, C1-C40 acylene, C4-C20 cycloalkylene, C4-C20 aralkylene, and C1- C40 alkoxyene, and R5 and R5’ are independently chosen from -H, substituted or unsubstituted C1-C40 alkyl, C2-C40 alkenyl, C4-C20 aryl, C1-C20 acyl, C4-C20 cycloalkyl, C4-C20 aralkyl, and C1- C40 alkoxy. Suitable polyols include, but are not limited to ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3- butanediol, 1,4-butanediol, 1,5-pentane- diol, 1,6-hexanediol, 2, 2- dimethyl- 1,3 -propanediol, 1,4- cyclohexanedimethanol, deca- methylene glycol, dodecamethylene glycol, glycerol, trimethylolpropane, and mixtures thereof. In some embodiments, the polyol is made via a ring opening polymerization, e.g. the ring opening polymerization of ε-caprolactone. Suitable polyester polyols include, but are not limited to, polybutylene adipate (PBAT, Tg of -30°C), polyethylene adipate, poly(diethylene glycol adipate), polyhexamethylene adipate, poly(neopentyl glycol) adipate, poly(butylene adipate-co-phthalate), polycaprolactone or copolymers thereof. Combinations of different polyester polyols may be used. In some embodiments, the polymer is prepared from a polyether polyol, including but not limited to, polyoxyalkylene polyols, polyoxycycloalkylene polyols, and alkylene oxide adducts thereof. In some embodiments, the polyether-polyols may be at least one of polyoxyethylene polyol (e.g. polyethylene glycol), polyoxypropylene polyol (e.g. polypropylene glycol), polyoxytetramethylene polyol (e.g. polyoxytetramethylene glycol), copolymers thereof and mixtures thereof and may have a hydroxyl functionality of from 2 to 6, in particular from 2 to 4, and in particular about 2. Polyether polyols are well known and may be prepared by reactions of compounds containing hydroxyl groups with, for example, ethylene oxide, propylene oxide, tetramethylene oxide in the presence of a base catalyst, yielding polyoxyethylene polyol, polyoxypropylene polyol and polyoxytetramethylene polyol, respectively. Copolymers containing at least two of ethylene oxide, propylene oxide and tetramethylene oxide may also be used. A variety of hydroxyl group containing compounds can be used to initiate the reaction including, for example, ethylene glycol, propylene glycol, butylene glycol, glycerine, 2,2-dimethylolpropane, pentaerythritol and the like. Examples of commercially available polyether polyols include Arcol polyether polyols available under the trade designation PPG 425, PPG 725, LHT 112 and LHT 240, (from Arco Chemical Co., Newtown Square, PA); polyethylene glycols such as those available under the trade designation Carbowax Sentry provided (Dow Chemical Co., Midland, MI); PLURACOL E 1450 polyethylene glycol (BASF Corp., Parsippany, NJ); and PolyTHF poly(tetramethylene oxide) polyol (BASF Corp., Parsippany, NJ). In some embodiments, the polyol may be a polycarbonate polyol. The polycarbonate polyol can be obtained from the reaction of aliphatic diols, such as 1,4-butanediol and 1,6-hexanediol, with phosgene, diaryl-carbonates such as diphenylcarbonate or with cyclic carbonates such as ethylene or propylene carbonate. The aliphatic diol may be any one of or combinations of the diols discussed with respect to Formula IV. In some embodiments, the polyol of the reactive mixture may be a hydroxyl terminated butadiene. The hydroxyl terminated butadiene may be a hydroxyl terminated polybutadiene and the polybutadiene may be a homopolymer or copolymer. In some embodiments, a hydroxy groups of the polymeric diol (e.g. polyether, polyester, polycarbonate, polybutadiene) polymer backbone may be reacted with or in otherwords end-capped with a compound comprising an isocyanto group and (meth)acrylate group, thereby forming a urethane (meth)acrylate. In other embodiments, the hydroxyl groups of the polymeric diol are reacted with a diisocyanate. Suitable diisocyanates includes a diisocyanate according to Formula V having the structure: In Formula V, R6 is chosen from substituted or unsubstituted C1-C40alkylene, C2-C40alkenylene, C4-C20arylene, C4-C20arylene-C1-C40alkylene-C4-C20arylene, C4-C20cycloalkylene, and C4-C20aralkylene. In some embodiments, the diisocyanate is chosen from dicyclohexylmethane-4,4’- diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-phenylene diisocyanate, 1,3- phenylene diisocyanate, m-xylylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, poly(hexamethylene diisocyanate), 1,4-cyclohexylene diisocyanate, 4-chloro-6-methyl-1,3-phenylene diisocyanate, 4,4’-diphenylmethane diisocyanate, 2,4’-diphenylmethane diisocyanate, 1,4- diisocyanatobutane, 1,8-diisocyanatooctane, 2,5-toluene diisocyanate, methylene bis(o-chlorophenyl diisocyanate, (4,4’-diisocyanato-3,3’,5,5’-tetraethyl) diphenylmethane, 4,4’-diisocyanato-3,3’- dimethoxybiphenyl (o-dianisidine diisocyanate), 5-chloro-2,4-toluene diisocyanate, 1-chloromethyl-2,4- diisocyanato benzene, tetramethyl-m-xylylene diisocyanate, 1,12-diisocyanatododecane, 2-methyl-1,5- diisocyanatopentane, 2,2,4-trimethylhexyl diisocyanate, or a mixture thereof. In some embodiments, the diisocyanate may be a chain extended diisocyanate, i.e. the reaction product of a diisocyanate and a dihydroxyl terminated oligomer or polymer, e.g. a dihydroxyl terminated, linear oligomer or polymer. During the reaction, excess diisocyanate is used to ensure that at least 80% by wt., 90% by wt., 95% by wt., 97% by wt.98% by wt., 99 wt. % by wt. or 99.5 wt. % of the product of the reaction is also a diisocyanate. The dihydroxyl terminated oligomer or polymer is not particularly limited and may include, for example, dihydroxyl terminated, linear polyesters and dihydroxyl terminated, linear polyethers. Polyester polyols, particularly polyester diols previously discussed with respect to the polyester polyols of the present disclosure may be used to form the chain extended diisocyanate. In some embodiments, the polyester polyol of the chain extended diisocyanate may include the reaction product of one or more C2-C12 diol and one or more C2-C12 diacid. In some embodiments, the diisocyanate includes a diphenylmethane diisocyanate, a reaction product of diphenylmethane diisocyanate and a hydroxyl terminated, linear oligomer or polymer, toluene diisocyanate, a reaction product of toluene diisocyanate and a hydroxyl terminated, linear oligomer or polymer and combinations thereof. The isocyanate terminated polymer may be end-capped with a compound comprising a hydroxyl group and a (meth)acrylate group, such an hydroxyl ethyl acrylate (HEA), thereby forming a urethane di(meth)acrylate polymer. One illustrative urethane di(meth)acrylate polymer comprising a (e.g. polypropylene oxide (PPO)) polyether backbone reacted with isophorone diisocyanate, and end-capped with HEA is depicted as follows: In some at 80, 85, 90, 95 wt.%, or greater of a polyether (e.g. PPO) backbone, reacted with 1 to 20 wt.% of an aliphatic isocyanate such as isophorone diisocyanate (IPDI), and end-capped with 0.5 to 10 wt.% of a hydroxy functional (meth)acrylate (such as hydroxyl ethyl acrylate). As the molecular weight of the polyether backbone increase, the wt.% of the reacted isocyanate and reacted hydroxy functional (meth)acrylate decreases. For example, when the molecular weight is about 50,000 g / mole, the amount of reacted isocyanate may be about 5 wt.% and the amount of reacted hydroxy functional (meth)acrylate may be about 1 wt.%. In another embodiment, the di(meth)acrylate polymer comprises at least 60, 65, 70 wt.%, or greater of a polyether (e.g. poly(tetramethylene oxide) backbone and 5 to 20 wt.% of non-polymeric diol such as 2-methylbutane diol reacted with 5 to 10 wt.% of an aliphatic (e.g. IPDI) isocyanate, and end- capped with 1 to 10 wt.% of a hydroxy functional (meth)acrylate (such as hydroxyl ethyl acrylate). In another embodiment, the di(meth)acrylate polymer comprises a polycaprolactone or polyester backbone reacted with 1.5 to 10 wt.% of an aliphatic isocyanate such as 4,4′-diisocyanato dicyclohexylmethane (H12MDI), and end-capped with 1 to 3 wt.% of a hydroxy functional (meth)acrylate (such as neopentyl glycol). The aliphatic urethane oligomer may be dissolved in a mixture of monomers such as 20-30 wt.% isobornyl acrylate and 25-35 wt.% tetrahydrofurfuyl acrylate, the amount of monomers based on the total amount of polymer and monomer (as provided by the supplier). Depending on viscosity of the (e.g. polyether, polyester, polycarbonate, polycaprolactone) urethane polymers, such polymers may be provided from commercial vendors dissolved in 5 - 35 wt.% of higher Tg diluting (meth)acrylate monomers such as isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate (THFA), cyclic trimethylolpropane formal acrylate (CTFA), hydroxypropyl acrylate (HPA), , neopentyl glycol diacrylate (NPGDA), tripropylene glycol diacrylate (TPGDA), and trimethylolpropane triacrylate (TMPTA). The di(meth)acrylate polymer may be aromatic or aliphatic. In some embodiments, the di(meth)acrylate polymer is aliphatic. In some embodiments, the di(meth)acrylate polymer comprises about two urethane moieties for each (meth)acrylate group. In some embodiments, the di(meth)acrylate polymer comprises about one urethane moieties for each (meth)acrylate group. In some embodiments, the di(meth)acrylate polymer is selected such that a homopolymer of the di(meth)acrylate polymer has a low glass transition temperature (Tg), i.e. no greater than 0, -10, -20, -30, - 40, or -50°C. The Tg of a homopolymer of the di(meth)acrylate polymer may be at least -80oC, -70oC, or -60oC. The Tg of various di(meth)acrylate polymers is typically reported by the supplier. The viscosity (e.g. at 60°C) can be indicative of the molecular weight. Other properties of a homopolymer of the di(meth)acrylate polymer are often reported by the supplier, such as tensile, elongation, and modulus. In one embodiment, the di(meth)acrylate polymer is very “soft and compliant” having a low tensile strength and modulus. In some embodiments, the tensile strength of a homopolymer of the di(meth)acrylate polymer is less than 1500, 1000, 750, 500, 250, or 100 psi. In some embodiments, the modulus of a homopolymer of the di(meth)acrylate polymer is less than 1500, 1000, 750, 500, 250, or 100 psi. Various di(meth)acrylate polymers having a molecular weight of 10,000 or greater are commercially available. Following is a table of commercially available di(meth)acrylate polymers and properties thereof (as reported by the supplier) utilized in the forthcoming examples: Table A - Di(meth)acrylate Polymers Tradename Tg°C by DSC Viscosity Tensile Modulus (cPs at 60°C) Strength / Elongation CN9018 Aliphatic -55 45,000 70 psi 110 psi Urethane Acrylate (Sartomer) Photomer 6645 -39 995 psi / Aliphatic Urethane 760% Acrylate (IGM Resins) CN9009 Aliphatic 40 3,000 4850 psi / 102,000 psi Urethane Acrylate 140% (Sartomer) CN9004 Aliphatic -76 21,000 315 psi 550 psi Urethane Acrylate (Sartomer) Following is a table of other commercially available higher molecular weight di(meth)acrylate polymers and properties thereof (as reported by the supplier). Table B - Di(meth)acrylate Polymers Tradename Tg°C Viscosity Tensile Modulus by (cPs at 60°C) Strength / DSC Elongation CN 9021 Aliphatic Urethane -54 32,000 at Acrylate (Sartomer) 25°C CN3211 Aliphatic Urethane -27 27,500 150 psi 175 psi Acrylate (Sartomer) CN9782 Aromatic Urethane -32 42,000 1100 psi 240 psi Acrylate (Sartomer) BR-345 Polyether diacrylate -42 42,000 (Bomar) BR-641E Polybutadiene -28 25,000 diacrylate (Bomar) Polycaprolactone diacrylate 500-50,000 (CM-Tec, Inc. Newark, DE) The composition typically comprises at least 15, 20, 25, 30, 35, 40, 45, 60, 55, 60, 65, 70, 75, or 80 wt.% di(meth)acrylate polymer(s), based on the total amount of ethylenically unsaturated components. In some embodiments, the composition comprises no greater than 80, 75, 70, 65, 60, 55, 50, 45, 40 or 35 wt.% of di(meth)acrylate polymer(s). In some embodiments, the di(meth)acrylate polymer(s) are aliphatic urethane acrylates. In some embodiments, the amount of di(meth)acrylate polymer(s) is greater than the amount of b) (e.g. low Tg) (meth)acrylate monomers. In some embodiments, the composition may further comprise an (e.g. aliphatic urethane) di(meth)acrylate polymer(s) having a weight average molecular weight of less than 10,000 g / mole., a higher Tg, or a combination thereof. In some embodiments, the composition may further comprise an (e.g. aliphatic urethane) di(meth)acrylate polymer(s) wherein a homopolymer thereof has a Tg of at least 0, 10, 20, 30, or 40°C, or greater than 40°C. In some embodiments, the tensile strength of a homopolymer of the lower molecular weight and / or higher Tg aliphatic urethane di(meth)acrylate polymer is greater than 1500, 2000, 3000, 4000, or 5000 psi. In some embodiments, the modulus of a homopolymer of the higher Tg di(meth)acrylate polymer is greater than 1500, 3000, 5000, 10,000; 25,000, 50,000; 75,000 or 100,000 psi. One illustrative higher Tg di(meth)acrylate polymer aliphatic urethane acrylate CN9009 described above. Various others higher Tg di(meth)acrylates including epoxy acrylates are commercially available. In some embodiments, the composition comprises at least 5, 6, 7, 8, 9, or 10 wt.% (e.g. aliphatic urethane) di(meth)acrylate polymer(s) having a lower molecular weight and / or higher Tg, based on the total amount of ethylenically unsaturated components. In some embodiments, the composition comprises no greater than 20, 15, or 10 wt.% of (e.g. aliphatic urethane) di(meth)acrylate polymer(s) having a lower molecular weight and / or higher Tg. The (e.g. aliphatic urethane) di(meth)acrylate polymer(s) typically lack acidic and / or amide moieties. (Meth)Acrylate and Ethylenically Unsaturated Monomers The composition comprises (meth)acrylate monomers, ethylenically unsaturated monomers (that improve adhesion and / or increase the modulus), or a combination thereof. The ethylenically unsaturated including (meth)acrylate monomers typically have a single (meth)acrylate group and a molecular weight no greater than 1500 or 1000 g / mole. The (meth)acrylate monomers are typically not derived from a polymeric diol and thus do not have a (e.g. polyester, polyether, polycarbonate, polycaprolactone, or polybutadiene) polymeric backbone. In some embodiments, the (e.g. aliphatic urethane) di(meth)acrylate polymer(s) is provided by a supplier dissolved in a mixture of (meth)acrylate monomer(s), as previously described. In some embodiments, the composition comprises one or more low Tg monomers, having a Tg no greater than no greater than 0, -10, -20, -30, -40, or -50°C. The Tg may be greater than -80oC, -70oC, or -60oC. The low Tg monomer may have the formula: H2C=CR1C(O)OR2wherein R1is H or methyl and R2is an alkyl with 1 to 22 carbons or a heteroalkyl with 2 to 20 carbons and 1 to 6 heteroatoms selected from oxygen or sulfur. The alkyl or heteroalkyl group can be linear, branched, cyclic, or a combination thereof. Exemplary low Tg monomers include for example ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2- methylbutyl acrylate, 2-ethylhexyl acrylate, 4-methyl-2-pentyl acrylate, n-octyl acrylate, 2-octyl acrylate, isooctyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, isotridecyl acrylate, octadecyl acrylate, and dodecyl acrylate. In some embodiments, the composition comprises at least one low Tg monomer having a non- cyclic alkyl (meth)acrylate monomer(s) having 4 to 20 carbon atoms. In some embodiments, the composition comprises at least one low Tg monomer having a (e.g. branched) alkyl group with 6 to 20 carbon atoms. In some embodiments, the low Tg monomer has a (e.g. branched) alkyl group with 7 or 8 carbon atoms. Exemplary monomers include, but are not limited to, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, 2-octyl (meth)acrylate, isodecyl (meth)acrylate, and lauryl (meth)acrylate. In some embodiments, the composition comprises at least 15, 20, 25, 30, 35, or 40 wt.% of low Tg (meth)acrylate monomers, based on the total amount of ethylenically unsaturated components (polymer(s) and monomer(s). In some embodiments, the composition comprises no greater than 60, 55, 50, 45, or 40 wt.% of low Tg (meth)acrylate monomers. Compositions comprising polymerized units of low Tg polymer in combination with low Tg monomer typically provide compositions with a low storage modulus. In some embodiments, the composition may comprise at least one high Tg monomer, having a Tg greater than 10oC and typically of at least 15oC, 20oC or 25oC, and preferably at least 50oC. High Tg monomer(s) may be included to increase the storage modulus (e.g. in place of a higher Tg urethane (meth)acrylate). Suitable high Tg alkyl (meth)acrylate monomers include, for example, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, stearyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate (110oC, according to Aldrich), norbornyl (meth)acrylate, benzyl methacrylate, 3,3,5 trimethylcyclohexyl acrylate, cyclohexyl acrylate, N-octyl acrylamide, and propyl methacrylate and combinations. In some embodiments, the composition comprises at least 5, 6, 7, 8, 9, or 10 wt.% of high Tg (meth)acrylate monomer(s), based on the total amount of ethylenically unsaturated components. In some embodiments, the composition comprises no greater than 20, 15, or 10 wt.% of high Tg (meth)acrylate monomer(s). In some embodiments, the high Tg monomer comprises isobornyl acrylate. In some embodiments, the composition comprises an acid functional monomer (a subset of high Tg monomers), where the acid functional group may be an acid per se, such as a carboxylic acid, or a portion may be salt thereof, such as an alkali metal carboxylate. Useful acid functional monomers include ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic acids, and mixtures thereof. Examples of such compounds include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, oleic acid, ^- carboxyethyl (meth)acrylate, 2-sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, vinylphosphonic acid, and mixtures thereof. Acidic monomers, such as acrylic acid (AA, Tg = 105°C) and 2-acrylamido-2-methylpropane sulfonic acid can improve adhesion. In some embodiments, the composition comprise non-acidic polar monomer. Useful non-acidic polar monomers include 2-hydroxyethyl (meth)acrylate; N-vinylpyrrolidone; N-vinylcaprolactam; acrylamide; mono- or di-N-alkyl substituted acrylamide; t-butyl acrylamide (Tg = 128°C); dimethylaminoethyl acrylamide; N-tert-octyl acrylamide (Tg = 83°C; poly(alkoxyalkyl) (meth)acrylates including 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, 2-methoxyethyl methacrylate, polyethylene glycol mono(meth)acrylates; alkyl vinyl ethers, including vinyl methyl ether; and mixtures thereof. Non-acid-functional polar monomers, such as N-vinylpyrrolidone (NVP, 168°C); N-vinylcaprolactam (NVC, 1.8°C); dimethyl acrylamide (DMAA, Tg = 81°C), N-tert-octylacrylamide (Tg = 83°C) can also improve adhesion. Some preferred (e.g. non-acidic) polar monomers comprising an amide moiety are depicted as follows: Alternative useful polar non-acidic ethylenically unsaturated monomers may comprise greater than one amide moiety. In one embodiment, the monomer is the Michael addition product(s) of N-vinyl monomers (e.g. having the molecular formula C16H26N2O2), and cyclic amide compounds, (e.g. having the molecular formulas C16H26N2O2 and / or C24H39N3O3. Such monomer may be used alone or in combinations with acidic monomers and / or non-acidic polar monomers, as described herein. Such monomers can also improve adhesion. In some embodiments, the (e.g. adhesive) composition typically comprises at least 10, 15, 20, 25, 30 wt.% of polar ethylenically unsaturated monomer(s), based on the total amount of ethylenically unsaturated components. The amount of polar ethylenically unsaturated monomer(s) is typically no greater than 40 or 35 wt.%. However, when the composition is a sealant, film or film layer, the composition may comprise little or no polar ethylenically unsaturated monomer(s). In some embodiments, the inclusion of polar ethylenically unsaturated monomers, such as those comprising an amide and / or acid moiety, have been found to provide improved adhesion, i.e. a rating of at least a “3” and preferably a “9” when tested with stainless steel, glass, polyester film, or a combination thereof (as further described in the forthcoming examples). Notably acrylic acid and many of the acrylamide ethylenically unsaturated monomers have a Tg of at least 50, 60, 70, 80, or 90°C. In some embodiments, the Tg, is no greater than 150, 140, 130, 120, 100 or 90°C. Inclusion of such monomers at sufficient amounts can raise the storage modulus. In some embodiment, non-acidic (e.g. amide- containing) monomers can be preferred (e.g. for metal substrates). In other embodiments, acidic monomers may be preferred (e.g. for transparent substrates). Notably AMPS can be difficult to solubilize, but is soluble in DMAA. In some embodiments, the amount AMPS is less than 20, 15, 10, or 5 wt.%. The ethylenically unsaturated monomers (including the (meth)acrylate monomers homopolymerize with themselves and copolymerize with the di(meth)acrylate polymer. Greater concentrations of ethylenically unsaturated polar monomers favor longer chain lengths of such. Although the higher molecular weight di(meth)acrylate may be characterized as a crosslinking monomer, the composition may optionally comprise other crosslinking monomers. Such crosslinking monomers typically have a molecular weight no greater than 1500 or 1000 g / mole. The crosslinking monomer may have at least two or three (meth)acrylate groups. Examples of useful multifunctional (meth)acrylate include, but are not limited to, di(meth)acrylates, tri(meth)acrylates, and tetra(meth)acrylates, such as 1,6-hexanediol di(meth)acrylate, poly(ethylene glycol) di(meth)acrylates, polybutadiene di(meth)acrylate, polyurethane di(meth)acrylates, and propoxylated glycerin tri(meth)acrylate, and mixtures thereof. Various other crosslinkers are known such as chlorinated triazines. Crosslinking monomer may be included to increase the storage modulus (e.g. in place of or in combination with a higher Tg (e.g. aliphatic urethane) di(meth)acrylate) polymer and / or high Tg (meth)acrylate monomer. The composition may optionally contain one or more conventional additives. Preferred additives include adhesion promoters (that are not polar ethylenically unsaturated monomers), tackifiers, plasticizers, dyes, antioxidants, UV absorbers, hindered-amine light stabilizers, coreshell rubbers and (e.g. inorganic) fillers such as (e.g. fumed) silica and glass bubbles. The composition may optionally comprise an organic solvent. Examples of solvent include ethyl acetate, n-butanol, isopropanol, acetone, acetic acid, benzene, toluene, ethylbenzene, isopropylbenzene, t- butylbenzene, heptane, cyclohexane, 1-chlorobutane, 1-bromobutane, and 1-iodobutane. However, in some embodiments the composition comprises little or no organic solvent, i.e. no greater than 5, 4, 3, 2, 1, 0.4, or 0.1 wt.% organic solvent. The composition can be polymerized by various techniques, yet is preferably polymerized by solventless radiation polymerization, including processes using electron beam, gamma, and especially visible and ultraviolet light radiation. The polymerizable composition typically comprises a photoinitiator. Useful photoinitiators include benzoin ethers such as benzoin methyl ether and benzoin isopropyl ether; substituted acetophenones such as 2,2-dimethoxy-2-phenylacetophenone photoinitiator, available under the trade name IRGACURE 651 or ESACURE KB-1 photoinitiator (Sartomer Co., West Chester, PA), and dimethylhydroxyacetophenone; substituted a-ketols such as 2- methyl-2-hydroxy propiophenone; aromatic sulfonyl chlorides such as 2-naphthalene-sulfonyl chloride; photoactive oximes such as 1-phenyl-1,2- propanedione-2-(O-ethoxy-carbonyl)oxime; mono- or bis- acrylphosphine oxides such as IRGANOX 819 or LUCIRIN TPO. In some embodiments, the composition may comprise a Norrish Type II photoinitiator for example camphorquinone. In such embodiments the composition may further comprise an amine co- initiator such as ethyl-4-(dimethylamino)benzoate. The polymerizable composition may comprise a combination of photoinitiators. Suitable photoinitiators are typically present in an amount from 0.1 to 3 wt. % The composition may be coated onto a substrate by a conventional coating method. Useful coating methods include for example roll knife coating, (e.g. comma) roll coating, dragging blade coating, reverse roll coating, winding bar (Mayer) coating, gravure roll coating, and slit-type die extrusion coating. The thickness of the (e.g. adhesive) composition on the substrate is typically at least 10, 25 or 50 microns. In some embodiments, the thickness is typically no greater than 2 mm, 1 mm, 750 microns, 500 microns, 250, 150, or 100 microns. In some embodiments, the composition irradiated with activating radiation in the range of 280 to 500 nanometers to polymerize the monomer component(s). UV light sources can be of various types. Low light intensity sources, such as blacklights, generally provide intensities ranging from 0.1 or 0.5 mW / cm2(millwatts per square centimeter) to 10 mW / cm2(as measured in accordance with procedures approved by the United States National Institute of Standards and Technology as, for example, with a UVIMAP UM 365 L-S radiometer manufactured by Electronic Instrumentation & Technology, Inc., in Sterling, VA). High light intensity sources generally provide intensities greater than 10, 15, or 20 mW / cm2ranging up to 450 mW / cm2or greater. In some embodiments, high intensity light sources provide intensities up to 500, 600, 700, 800, 900 or 1000 mW / cm2. UV light to polymerize the monomer component(s) can be provided by various light sources such as light emitting diodes (LEDs), blacklights, medium pressure mercury lamps, etc., or a combination thereof. The ethylenically unsaturated polymer and monomer component(s) can also be polymerized with higher intensity light sources as available from Fusion UV Systems Inc., Gaithersburg, MD. The UV exposure time for polymerization and curing can vary depending on the intensity of the light source(s) used. For example, complete curing with a low intensity light course can be accomplished with an exposure time ranging from about 30 to 300 seconds, whereas complete curing with a high intensity light source can be accomplished with shorter exposure time ranging from about 5 to 20 seconds. Partial curing with a high intensity light source can typically be accomplished with exposure times ranging from about 2 seconds to about 5 or 10 seconds. The physical properties of the cured (e.g. adhesive) composition can be characterized by various techniques including Dynamic Mechanical Analysis. In some embodiments the cured composition has a peak tan delta less than 30, 25, 20, 15, 10, 5, 0, -5, -10, or -15°C. In some embodiments, the peak tan delta is at least -50, -40, -30, or -20°C. In some embodiments, the peak tan delta is at least -10 or 0°C. In some embodiments, the cured composition has an elastic modulus (E’) at 0°C of less than 200, 150, 100, 50, or 25 MPa. In some embodiments, the cured composition has an elastic modulus (E’) at 0°C of at least 5, 10, 15, 20, 25, 50, or 75 MPa. In some embodiments, the cured composition has an elastic modulus (E’) at -20°C of less than 1500, 1000, 500, 250 or 100 MPa. In some embodiments, the cured composition has an elastic modulus (E’) at -20°C of at least 20, 25, 50, 100, 250, 500, or 1000 MPa. In some embodiments, the cured composition has an elastic modulus (G’) at 25°C of greater than 0.3, 1, 5, 10 of 15 MPa (indicative that the cured composition is not a pressure sensitive adhesive), Substrates The composition may be applied to various organic and inorganic substrates including but not limited to polymeric films, woven or nonwoven fabrics, foams, metal foils, glass (including electronic glass), ceramic, and combinations thereof (e.g. metalized polymeric film). The metal foils and metalized polymeric films may comprise metals such as aluminum, titanium, stainless steel, and copper. Polymeric films include for example polyolefins such as polypropylene (e.g. biaxially oriented), polyethylene (e.g. high density or low density), polyvinyl chloride, polyurethane, polyester (polyethylene terephthalate), polycarbonate, poly(meth)acrylic polymers including polymethyl(meth)acrylate (PMMA), polyvinylbutyral, polyimide, polyamide, ABS (acrylonitrile-butadiene-styrene copolymer, fluoropolymer, cellulose acetate, cellulose triacetate, ethyl cellulose, as well as bio-based material such as polylactic acid (PLA). The woven or nonwoven fabric may comprise fibers or filaments of synthetic or natural materials such as cellulose (e.g. tissue), cotton, nylon, polyethylene, rayon, glass, ceramic materials, and the like. In some embodiments, the substrate is a transparent film having a transmission of visible light of at least 90 percent. In other embodiments, the second backing is opaque (e.g. white) or reflective. The thickness of the film is typically at least 10, 15, 20, or 25 microns (1 mil) and typically no greater than 500 microns (20 mil) thickness. In some embodiments, the thickness of the film or second backing is no greater than 400, 300, 200, or 100 microns. The film may have the same thickness as the second backing. However, the film, particularly when utilized in combination with a backing, may have a thickness of less than 10 microns. In some embodiments, the film comprising the (meth)acrylic polymer and polyvinyl acetal polymer is typically at least 250 nm, 500 nm, 750 nm or 1 micron. The overall film as well as the second backing is typically in the form of a roll-good but may also be in the form of individual sheets. In some embodiments, the composition may be characterized as a structural adhesive. In some embodiments, an article is described that further comprises a second substrate and the structural adhesive described herein bonds the substrate to the second substrate. Various combinations of substrates comprised of organic polymer films, metals, glass, and coated glass, where coatings may be comprised of acrylic, epoxy, and urethane functionalities, as previously described may be bonded with the cured structural adhesive composition. In some embodiments, the substrates are a component of an electronic device such as an electronic display, tablet, or cell phone. The substrate may optionally further comprise a primer or adhesion-promoting treatment. Examples of suitable primers include chlorinated polyolefins, polyamides, and modified polymers disclosed in U.S. Pat. Nos.5,677,376, 5,623,010 and those disclosed in WO 98 / 15601 and WO 99 / 03907, and other modified acrylic polymers. The film and / or second backing may also be subjected to an adhesion- promoting treatment such as air or nitrogen corona treatment, plasma, flame, or actinic radiation. Objects and advantages of this invention are further illustrated by the following examples. The particular materials and amounts, as well as other conditions and details, recited in these examples should not be used to unduly limit this invention. Table 1. Materials Used Abbreviation Description Source 2-EHA 2-Ethyl Hexyl Acrylate (CAS # 103-11-7) BASF M140 Phenoxyethyl Acrylate (CAS # 48154-04-6) Miwon CN9018 Urethane Diacrylate Polymer Sartomer CN9009 Urethane Diacrylate Polymer Sartomer Photomer 6645 Urethane Diacrylate Polymer IGM Resins CN9004 Urethane Diacrylate Polymer Sartomer BR641E Polybutadiene Urethane Diacrylate Polymer Bomar AA Acrylic Acid (CAS # 79-10-7) BASF M1112 Cyclic Trimethylolpropane Formal Acrylate (CTFA) (CAS # 66492-51-1) Miwon M100D Caprolactone acrylate, (CAS #110489-05-9) Miwon LA Lauryl acrylate BASF M1151 Monofunctional Cyclic Methacrylate (CAS # 46729-07-1) Miwon 4-HBA 4-Hydroxy Butyl Acrylate (CAS # 2478-10-6) TCI DMAA N,N-Dimethyl Acrylamide (CAS # 2680-03-7) TCI VMOX Vinyl methyl oxazolidinone (VMOX®) (CAS # 3395-98-0) BASF NTOAA N-t-Octyl-Acrylamide (CAS #4223-03-4) Nouryon NVP N-Vinyl Pyrrolidone (CAS #125304-04-3) TCI NVC N-Vinyl Caprolactam (CAS #2235-00-9) – Liquid (l) grade BASF AMPS 2-Acrylamido-2-methylpropane sulfonic acid (CAS # 15214-89-8) Alfa Aesar DMAEA N,N-Dimethyl Aminoethyl Acrylate (CAS # 2439-35-2) Sigma Aldrich DEAEA N,N-Diethyl Aminoethyl Acrylate (CAS # 2426-54-2) Sigma Aldrich Photoinitiator - Phenylbis(2,4,6-trimethyl benzoyl) Irg 819 phosphine oxide known as Irgacure 819 or Omnirad Sigma Aldrich 819 from IGM H18 Thixotrope - Hydrophobic surface treated fumed silica Wacker Formulation Preparation: AMPS Stock: The AMPS monomer was dissolved into DMAA at 16 wt % under stirring in a glass vial at 100 °C on the hotplate. After dissolution the pale-yellow solution was stable, and the AMPS remained in solution. This was used as a carrier for AMPS monomer. Any additional DMAA required in the formulation could be added neat. Resin Stock: To dilute the viscous Urethane acrylate oligomers CN9018 and CN9009 for easier usage they were combined with 2-EHA in a 200 MAX polypropylene mixing cup (from FlackTek, Inc., Landrum, SC). To this was added photoinitiator Irg 819 and H18 fumed silica. Formulation was mixed on a SPEEDMIXER DAC 600.2 VAC-P (Hauschild SpeedMixer Inc., Farmington Hills, MI) for 30 s at 1200 revolutions per minute (rpm),5 min at 2350 rpm, 30 s at 1200 rpm under reduced pressure 20 mBar for vacuum assisted degassing of the stock. This produced a homogenous spreadable paste used as is. See Table 2 for Resin Stock Details. Formulations Described in Table 3a: Using a base of 4.5 g of Resin Stock described in Table 2 the remaining 2-EHA and adhesion promoting monomers or additives were charged to a 40 MAX polypropylene mixing cup (from FlackTek, Inc., Landrum, SC). See Table 3a. for formulation details. Formulation was mixed on a SPEEDMIXER DAC 150 FVZ (Hauschild SpeedMixer Inc., Farmington Hills, MI) for at least 60 s at 2500-3000 revolutions per minute (rpm). Once homogenized the formulation was used for adhesion evaluation. Formulations Described in Tables 3b and 3c: To a 40 MAX polypropylene mixing cup (from FlackTek, Inc., Landrum, SC) the raw materials recorded in Table 3b. were added. Formulation was mixed on a SPEEDMIXER DAC 150 FVZ (Hauschild SpeedMixer Inc., Farmington Hills, MI) for at least 60 s at 2500-3000 revolutions per minute (rpm). Once homogenized the formulation was for adhesion evaluation. Table 2. Resin Stock Composition – Mass Fraction Resin Stock CN9018 71.61 CN9009 8.98 2-EHA 12.20 H18 5.45 IC819 1.76 Total 100 Table 3a. Example Compositions – Mass Fraction Adhesion Promoter Ex. CN9018 CN9009 2 EHA ID Charge AMPS H18 Irg 819 Ex-1 36.7 4.6 27.5 DMAA 27.5 0 2.8 0.9 Ex-2 32.8 4.1 31.2 NVP 28.6 0 2.5 0.8 Ex-3 32.8 4.1 31.2 NVC (l) 28.6 0 2.5 0.8 Ex-4 32.8 4.1 31.2 VMOX 28.6 0 2.5 0.8 Ex-5 32.8 4.1 31.2 NTOAA 28.6 0 2.5 0.8 Ex-6 36.1 4.5 27 DMAA 27.0 1.7 2.7 0.9 Ex-7 34.9 4.4 26.1 DMAA 26.1 5 2.6 0.9 Ex-8 36.3 4.5 32.2 DMAA 22.0 1 2.7 0.9 Ex-9 36.1 4.5 36.1 DMAA 18.0 1.8 2.7 0.9 Ex-10 32.8 4.1 31.2 DMAA / NTOAA 14.3 ea. 0 2.5 0.8 Ex-11 32.8 4.1 39.2 AA 20.6 0 2.5 0.9 CE-1 36.7 4.6 27.5 M140 27.5 0 2.8 0.9 CE-2 32.8 4.1 31.2 DMAEA 28.6 0 2.5 0.9

[0002] Table 3b. Example Compositions – Mass Fraction Ex.rem4o0A to 5 09A A A2 DA91B1 0h 4A O 6 N8H11018P6C H E A T M L N DCI-4M M1H Ex-12 60.5 18.6 20.0 0.9 Ex-13 60.8 22.0 16.1 1.1 Ex-14 41.1 17.5 23.0 0.8 17.5 Ex-15 39.9 16.8 24.0 1.0 18.3 Ex-16 39.3 13.1 28.0 0.9 18.7 Ex-17 19.2 53.0 19.0 0.9 4.8 2.9 Table 3c. Example Compositions – Mass Fraction Ex. BR641E M1151 LA DMAA VMOX IC819 Ex-18 39.6 14.9 24.8 19.8 1 Ex-19 39.6 14.9 24.8 19.8 1 Ex-20 44.6 12.4 22.3 19.8 1 Ex-21 44.6 12.4 22.3 19.8 1 Adhesion Button Preparation and Evaluation: Stainless Steel (SS): SS overlap shear panels were cleaned with MEK, and IPA, wiped with a Kimwipe, and allowed to dry for at least 3 min. Then, a 0.75 mm thick rubber mold with four 14 mm circle cut outs was placed on the SS substrate. The SS substrate was placed on top of a 5 mm thick aluminum plate. A portion of the formulation was dotted onto the SS substrate inside the 14 mm circles. The formulations were then covered with a release liner followed by a 5 mm thick glass plate. The assembly described was then placed under a Clearstone CT2000 450 nm LED light source with OD 5+ optical shielding and irradiated 2 min @ 16 % power 268 mW / cm2(ref to Speedre SDR420L radiometer, or 350 mW / cm2with respect to (w. r. t.) ILT-800 radiometer). The thickness of the cured composition was about the same as the thickness of the rubber mold (i.e.0.75 mm). The warm samples were quenched to ambient temperature on a cool SS Plate before evaluating. The release liner and rubber mold were removed from the cured adhesive discs. Then the adhesion was evaluated by initiating cleavage between the substrate and the cured adhesive disc. Followed by assessing the resistance of a 90 ° peel by hand. Adhesion was evaluated qualitatively using a ranking system of (best) 9, 3, 1, -1, - 3 (worst). Specimens were prepared multiple times and given their rankings in a round robin type evaluation scheme. Glass & PET (unprimed): Glass slides were cleaned with IPA, wiped with a Kimwipe, and allowed to dry for at least 3 min. Then, a 0.75 mm thick rubber mold with four 14 mm circle cut outs was placed on the glass substrate. The glass substrate was placed on top of a 5 mm thick aluminum plate. A portion of the formulation was dotted onto the Glass substrate inside the 14 mm circles. The formulations were then covered with a PET (unprimed) liner followed by a 5 mm thick glass plate. The assembly described was then placed under a Clearstone CT2000 450 nm LED light source with OD 5+ optical shielding and irradiated 2 min @ 16 % power 268 mW / cm2(ref to Speedre SDR420L radiometer,or 350 mW / cm2w.r.t. ILT-800 radiometer). The thickness of the cured composition was about the same as the thickness of the rubber mold (i.e.0.75 mm). The warm samples were quenched to ambient temperature on a cool SS Plate before evaluating. Removal of the PET liner from the cured adhesive discs was first evaluated. Noting if the cured adhesive stayed with the PET or the glass and the resistance to remove it with a 90 ° peel as described above for SS. If the cured adhesive discs remained on the glass the adhesion was subsequently evaluated as described above for SS. Table 4. Adhesion Ranking Ex. Rank SS Rank Rank PET glass AMPS (wt %) Adh. Prom. wt % Ex-1 3- DMAA 27.5Ex-2 3 9 9-NVP 28.6Ex-3 9 9 9-NVC (l) 28.6Ex-4 3 9 9-VMOX 28.6Ex-5 3 3 3-NTOAA 28.6Ex-6 9 3 9 1.7 DMAA 27 Ex-7 9 1 9 5 DMAA 26.1 Ex-8 3 3 3 1 DMAA 22 Ex-9 1 3 3 1.8 DMAA 18 Ex-10 3 3 3-DMAA / NTOAA 14.3 ea.Ex-11 3 1 9-AA 20.6CE-1 -1 1 -1-M140 27.5CE-2 -1 -1 1-DMAEA 28.6Ex-12 3 9 3- DMAA19.98Ex-13 1 9 3- DMAA16.2Ex-143 1 3- DMAA 23Ex-151 1 1- DMAA 24 Ex-16 1 1 3 - DMAA 28 Ex-18 9 3 9 - DMAA 19.8 Ex-19 3 9 3 - VMOX 19.8 Ex-20 9 9 9 - DMAA 19.8 Ex-21 3 9 3 - VMOX 19.8 Samples of the cured composition were prepared by coating between two release coated polyester films (3 mil) at a thickness of 0.4- 0.7 mm. The films were placed on top of a 5 mm thick aluminum plate and covered with a 5 mm glass plate. The assembly described was then placed under a Clearstone CT2000450 nm LED light source with OD 5+ optical shielding and irradiated 2 min @ 16 % power 268 mW / cm2(ref to Speedre SDR420L radiometer, or 350 mW / cm2w.r.t. ILT-800 radiometer). The cured compositions had their mechanical properties measured on a Dynamic Mechanical Analyzer (DMA) using a Q850 DMA from TA Instruments. Strips of material approximately 12x6x0.6 mm were cut out of a cured film and mounted onto the DMA for testing in a tensile mode. Temperature ramps were run at a rate of 3 C / min from –60Cto 60 C. The modulus at three temperatures is listed in Table 5 along with the peak of tan delta (Tg) of the material. For determining material modulus in a form where a continuous uniform strip of material is unavailable for DMA testing nanointendation testing following ASTM E 2546 can be used to provide similar modulus data. Table 5. Example Composition Moduli by DMA Temp Ramp Ex. E´ (MPa) @ -20 °C E´ (MPa) @ 0 E´ (MPa) @ °C 25 °C Peak Tan δ (° C) Ex-2 240 43.4 5.73 6.9 Ex-3 344 100 7.95 20.8 Ex-4 373 126 15.4 18.1 Ex-5 233 26.5 1.03 9.1 Ex-6 102 14.1 2.68 -3.7 Ex-7 130 21.1 3.73 3.1 Ex-8 79.6 6.9 1.14 -3.8 Ex-9 25.7 2.68 0.9 -16.9 Ex-10 256 33.3 1.29 10.3 Ex-11 686 30.6 2.07 6.3 CE-1 14.9 1.19 0.76 -18.9 Ex-12 1130 323 3.57 16.7 Ex-13 863 89.2 1.66 10.1 Ex-17 36.3 1.92 0.88 -12.4 Ex-21 204 36.3 1.43 13.5

Claims

What is claimed is:

1. An article comprising a composition bonded to a substrate; wherein the composition comprises: a) at least 15 wt.% of polymerized units of polymer(s) having a weight average molecular weight of 10,000 to 100,000 g / mole and at least two (meth)acrylate groups; b) at least 15 wt.% of a polymerized units of (meth)acrylate monomer(s); c) 10 to 40 wt.% of polymerized units of ethylenically unsaturated monomer(s) comprising a moiety selected from acidic moieties, amide moieties, or a combination thereof.

2. The article of claim 1 wherein the polymer(s) have a Tg less than 0°C or -25°C.

3. The article of claims 1-2 wherein the polymer(s) have a weight average molecular weight of at least 15,000; 20,000; 25,000; 30,000; 35,000, 40,000; 45,000, or 50,000 g / mole.

4. The article of claims 1-3 wherein the composition comprises at least 20, 25, 30, 35, 40, 45, 50, 55, 60 wt.% of polymerized units of the polymer(s).

5. The article of claims 1-4 wherein the polymer(s) comprises a backbone selected from polyether, polyester, polybutadiene, polycarbonate, or polycaprolactone and optionally urethane moieties.

6. The article of claims 1-5 wherein b) comprises at least one (meth)acrylate monomer wherein a homopolymer thereof has a Tg less than 0°C or -25°C.

7. The article of claim 6 wherein the composition comprises less than 40, 35, 30, 25, 20, or 15 wt.% of polymerized units of (meth)acrylate monomer wherein a homopolymer thereof has a Tg less than 0°C or -25°C.

8. The article of claims 1-7 wherein the composition further comprises at least one (meth)acrylate polymer or monomer wherein a homopolymer thereof has a Tg greater than 25, 30, 35, or 40°C.

9. The article of claim 8 wherein the at least one (meth)acrylate monomer or polymer has a molecular weight less than 10,000; 5,000; or 2,500 g / mole.

10. The article of claims 1-9 wherein c) comprises N,N-dimethyl acrylamide, an ethylenically unsaturated monomer comprising a nitrogen-containing cycloaliphatic group, a (meth)acrylamide monomer comprising an acidic group or a C4-C12 alkyl group, or a combination thereof.

11. The article of claim 1-10 wherein the composition has one or more of the following properties:a peak tan delta less than 25 or -0°C; an elastic modulus (E’) at 0°C of less than 200, 150, 100, 50, or 25 MPa; an elastic modulus (E’) at -20°C of less than 1500, 1000, 500, 250 or 100 MPa; an elastic modulus (G’) at 25°C of greater than 0.3, 1, 5, 10 of 15 MPa.

12. The article of claims 1-11 wherein the composition is at least a semi-structural adhesive.

13. The article of claims 1-12 wherein the article further comprises a second substrate and the adhesive bonds the substrate to the second substrate.

14. The article of claims 1-13 wherein the substrate and second substrate are independently selected from an organic polymer film, metal, or glass.

15. A composition comprising: a) at least 15 wt.% of a polymer(s) having a weight average molecular weight of 10,000 to 100,000 g / mole and at least two (meth)acrylate groups; b) at least 15 wt.% of (meth)acrylate monomer(s); c) 10 to 40 wt.% of polymerized units of ethylenically unsaturated monomer(s) comprising a moiety selected from acidic moieties, amide moieties, or a combination thereof.

16. The composition of claim 15 further characterized by claims 2-12.

17. A composition comprising: a) at least 15 wt.% of a polymer(s) having a weight average molecular weight of 10,000 to 100,000 g / mole and at least two (meth)acrylate groups; and b) 10 to 40 wt.% of polymerized units of ethylenically unsaturated monomer(s) comprising a moiety selected from acidic moieties, amide moieties, or a combination thereof.

18. The composition of claim 17 further characterized by claims 2-12.

19. A composition comprising: a) at least 15 wt.% of a polymer(s) having a weight average molecular weight of 10,000 to 100,000 g / mole and at least two (meth)acrylate groups; b) at least 15 wt.% of (meth)acrylate monomer(s) wherein a homopolymer thereof has a Tg less than 0°C; wherein the weight of a) is greater than the weight of b); c) optionally polymerized units of ethylenically unsaturated monomer(s) comprising a moiety selected from acidic moieties, amide moieties, or a combination thereof.5 20. The composition of claim 19 further characterized by claims 2-12.

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