US 20080026662A1 (19) United States (12) Patent Application Publication (10) Pub. N0.: US 2008/0026662 A1 Ramsey (43) Pub. Date: Jan. 31, 2008

(54) FLEXIBLE SURFACE HAVING A UV Related U.s. Application Data CURABLE WATERPROOFING (63) Continuation-in-part of application No. 11/459,876, COMPOSITION ?led on Jul. 25, 2006. (75) Inventor: Sally Judith Weine Ramsey, Publication Classi?cation Tallmadge, OH (U S) (51) Int. Cl. D04H 1/00 (2006.01) Correspondence Address: A01N 25/00 (200601) WILSON SONSINI GOODRICH & ROSATI (52) US. Cl...... 442/376; 424/405; 427/404 650 PAGE MILL ROAD (57) ABSTRACT PALO ALTO, CA 94304-1050 Disclosed are thixotropic compositions that are curable using ultraviolet and Visible radiation. In addition, methods (73) Assignee: ECOLOGY COATINGS, INC., . . . Akron’ OH (Us) of applying the compositions to ?ber substrates such as are described, as are methods of curing the coated products. Partially or fully Water-resistant articles made (21) APP1- N04 11/684,502 using these compositions, such as snoW melting mats, Wind shield protectors, and freezer defrosting sheets are also (22) Filed: Mar. 9, 2007 disclosed

32 Patent Application Publication Jan. 31, 2008 Sheet 1 0f 4 US 2008/0026662 A1 Patent Application Publication Jan. 31, 2008 Sheet 2 0f 4 US 2008/0026662 A1 Patent Application Publication Jan. 31, 2008 Sheet 3 0f 4 US 2008/0026662 A1 Patent Application Publication Jan. 31, 2008 Sheet 4 0f 4 US 2008/0026662 A1 US 2008/0026662 A1 Jan. 31, 2008

FLEXIBLE SURFACE HAVING A UV [0013] (d) at least one acrylate, methacrylate, diacry CURABLE WATERPROOFING late, dimethacrylate, triacrylate and/or trimethacrylate COMPOSITION monomer, Wherein the acrylate is other than tetrahy drofurfuryl acrylate, in an amount of about 2% by CROSS-REFERENCE TO RELATED Weight up to about 80% by Weight; APPLICATIONS [0014] (e) a cross-linkable, silicone acrylate, silicone [0001] This application is a Continuation-in-Part of Us. methacrylate, silicone diacrylate, silicone dimethacry application Ser. No. 11/459,876, ?led Jul. 25, 2006, Which is late, silicone triacrylate and/ or silicone trimethacrylate; incorporated by reference herein in its entirety. [0015] (f) at least one metal salt comprising: [0016] a cation selected from among Li", Na", K", FIELD OF THE INVENTION Mg“, Ca“, A13", Zn2+, Mn“, and Ag"; and [0017] an anion selected from among F“, Cl“, Br“, I“, [0002] Described herein are 100% solids, UV curable C032‘, C104- and N03‘; and compositions for use in adhesion, repair and architecture. [0018] (g) optionally, a pigment, pigment dispersion Also disclosed are articles of manufacture that include the and/or a third photo-initiator; UV curable and/or UV cured compositions described herein. [0019] Wherein the composition is: BACKGROUND OF THE INVENTION [0020] (i) actinic-radiation curable; and [0021] (ii) thixotropic With an apparent viscosity at [0003] A variety of consumer, scienti?c, and industrial room temperature greater than about 5000 centi products have some type of coating, Which has been applied poise. in order to ful?ll some expected function, utility and/or [0022] In one embodiment is a coated mat Wherein the appearance. Coating such products With solvent based coat ?brous substrate comprises recycled paper. In another ings can be problematic due to environmental issues stem embodiment is a coated mat Wherein the coating is impreg ming from evaporation of the volatile solvent. Also, such nated into the ?brous substrate. In a further embodiment is coatings can require thermal curing, resulting in the need for a coated mat comprising silica gel. In yet a further embodi curing ovens, and the associated energy expenditure to ment is a coated mat comprising at least one salt. In one operate them. Adhesives and sealants typically contain vola embodiment is a coated mat Wherein the at least one salt is tile solvents that are harmful and/or toxic to the environment selected from the group consisting of NaCl, CaCl2, MgCl2, and user. Disclosed herein are 100% solids, UV curable and an organic salt. In another embodiment is a coated mat compositions for use in architecture, adhesion and repair. Wherein the organic salt is a carboxylate salt. In another embodiment is a coated mat Wherein the coated mat is SUMMARY OF THE INVENTION formed into an item selected from the group consisting of a [0004] Provided herein are compositions that are 100% snoW melting mat, a freeZer defrosting mat, a Windshield solids. Compositions provided herein do not include toxic, cover, and shelf paper. environmentally harmful, volatile solvents that need to be [0023] In one aspect is a method of preparing a mat for evaporated and/or driven off to affect curing. Compositions melting snoW, comprising: provided herein are thixotropic, With an apparent viscosity at [0024] coating or impregnating a mat With UV curable room temperature of about 5000 centipoise. Compositions Waterproo?ng formulation comprising: provided herein are UV curable. Compositions provided [0025] (a) SiO2 nano-?llers; herein do not contain any Water or organic solvent, Which [0026] (b) a benZoyldiphenylphosphine oxide photo must be removed before complete curing is achieved. There initiator and an ot-hydroxyketone photo-initiator; fore, the compositions provided herein are less haZardous to [0027] (c) tetrahydrofurfuryl acrylate; the environment, and are economical because they require [0028] (d) at least one acrylate, methacrylate, diacry less space, less energy, and less time to cure. Compositions late, dimethacrylate, triacrylate and/or trimethacrylate provided herein can be applied to objects as a single coat. In monomer, Wherein the acrylate is other than tetrahy some embodiments, compositions provided can be applied drofurfuryl acrylate, in an amount of about 2% by to objects in more than one coat, such as, for example, tWo Weight up to about 80% by Weight; coats, or more than tWo coats. Compositions provided herein [0029] (e) a cross-linkable, silicone acrylate, silicone lack solvents and are thus considered environmentally methacrylate, silicone diacrylate, silicone dimethacry friendly. Compositions provided herein do not require ther late, silicone triacrylate and/ or silicone trimethacrylate; mal curing, or drying stages With coatings of the composi [0030] (f) at least one metal salt comprising: tions, and thus there is no need for large ovens, Which decreases the space and energy commitment of the coating [0031] a cation selected from among Li", Na", K", end-user. Mg“, Ca“, A13", Zn“, Mn“, and Ag"; and [0005] In one aspect is a coated mat comprising: [0032] an anion selected from among F‘, Cl‘, Br‘, I‘, [0006] a sheet of a ?brous substrate; C032“, C104“ and N03“; and [0007] a coated top layer; and [0033] (g) optionally, a pigment, pigment dispersion [0008] a coated bottom layer; and/or a third photo-initiator; [0009] Wherein the coating comprises: [0034] Wherein the composition is: [0010] (a) SiO2 nano-?llers; [0035] (i) actinic-radiation curable; and [0011] (b) a benZoyldiphenylphosphine oxide photo [0036] (ii) thixotropic With an apparent viscosity at initiator and an ot-hydroxyketone photo-initiator; room temperature greater than about 5000 centi [0012] (c) tetrahydrofurfuryl acrylate; poise; and US 2008/0026662 A1 Jan. 31, 2008

[0037] coating at least one side of the mat With a compo [0069] Wherein the composition is: sition comprising: [0070] (i) actinic-radiation curable; and [0038] from about 0% to about 25% powdered silica [0071] (ii) thixotropic With an apparent viscosity at gel; and room temperature greater than about 5000 centi poise; and [0039] from about 75% to about 100% salt. [0072] a coating layer comprising from about 0% to about [0040] In one aspect is a freezer defrosting mat, compris 25% poWdered silica gel and about 75% to about 100% salt. ing: [0073] In one embodiment is a vehicle Windshield cover, [0041] a ?brous substrate; further comprising a means to attach the vehicle Windshield [0042] a coating layer, Wherein the coating comprises a cover to the Windshield. In another embodiment is a vehicle UV curable Waterproo?ng formulation comprising: Windshield cover Wherein the means to attach the vehicle [0043] (a) SiO2 nano-?llers; Windshield cover is by use of multiple magnets attached near [0044] (b) a benZoyldiphenylphosphine oxide photo the edges of the Windshield cover. [0074] In one aspect is an insect-resistant liner for lining initiator and an ot-hydroxyketone photo-initiator; shelves, comprising [0045] (c) tetrahydrofurfuryl acrylate; [0075] a ?brous substrate; [0046] (d) at least one acrylate, methacrylate, diacry [0076] a coating layer, Wherein the coating comprises a late, dimethacrylate, triacrylate and/or trimethacrylate UV curable Waterproo?ng formulation comprising: monomer, Wherein the acrylate is other than tetrahy [0077] (a) SiO2 nano-?llers; drofurfuryl acrylate, in an amount of about 2% by [0078] (b) a benZoyldiphenylphosphine oxide photo Weight up to about 80% by Weight; initiator and an ot-hydroxyketone photo-initiator; [0047] (e) a cross-linkable, silicone acrylate, silicone [0079] (c) tetrahydrofurfuryl acrylate; methacrylate, silicone diacrylate, silicone dimethacry [0080] (d) at least one acrylate, methacrylate, diacry late, silicone triacrylate and/ or silicone trimethacrylate; late, dimethacrylate, triacrylate and/or trimethacrylate [0048] (f) at least one metal salt comprising: monomer, Wherein the acrylate is other than tetrahy drofurfuryl acrylate, in an amount of about 2% by [0049] a cation selected from among Li", Na", K", Weight up to about 80% by Weight; Mg“, Ca“, A13", Zn“, Mn“, and Ag"; and [0081] (e) a cross-linkable, silicone acrylate, silicone [0050] an anion selected from among F“, Cl“, Br“, I“, methacrylate, silicone diacrylate, silicone dimethacry C032“, C104“ and N03“; and late, silicone triacrylate and/ or silicone trimethacrylate; [0051] (g) optionally, a pigment, pigment dispersion [0082] (f) at least one metal salt comprising: and/or a third photo-initiator; [0083] a cation selected from among Li", Na", K", [0052] Wherein the composition is: Mg“, Ca“, A13", Zn“, Mn“, and Ag"; and [0053] (i) actinic-radiation curable; and [0084] an anion selected from among F“, Cl“, Br“, I“, CO3“, C104- and NO3i; and [0054] (ii) thixotropic With an apparent viscosity at [0085] (g) optionally, a pigment, pigment dispersion room temperature greater than about 5000 centi and/or a third photo-initiator; poise; and [0086] Wherein the composition is: [0055] a coating layer comprising at least one salt. [0087] (i) actinic-radiation curable; and [0056] In one embodiment is a freeZer defrosting mat [0088] (ii) thixotropic With an apparent viscosity at Wherein the at least one salt is an organic salt. room temperature greater than about 5000 centi [0057] In one aspect is a vehicle Windshield cover to poise; and prevent snoW or ice buildup, comprising: [0089] a coating layer comprising [0090] from about 0% to about 100% poWdered silica [0058] a ?brous substrate; gel; [0059] a coating layer, Wherein the coating comprises a [0091] from about 0% to about 100% borax; and UV curable Waterproo?ng formulation comprising: [0092] from about 0% to about 100% boric acid. [0060] (a) SiO2 nano-?llers; [0093] In one aspect is a method of deterring insect [0061] (b) a benZoyldiphenylphosphine oxide photo infestation in shelving, comprising lining the shelving With initiator and an ot-hydroxyketone photo-initiator; an insect-resistant liner described herein. In one embodi [0062] (c) tetrahydrofurfuryl acrylate; ment is a method of deterring insect infestation in shelving [0063] (d) at least one acrylate, methacrylate, diacry Wherein the shelving is foodstuff shelving. [0094] In certain embodiments, provided herein are com late, dimethacrylate, triacrylate and/or trimethacrylate positions comprising: monomer, Wherein the acrylate is other than tetrahy [0095] (a) SiO2 nano-?llers; drofurfuryl acrylate, in an amount of about 2% by [0096] (b) a benZoyldiphenylphosphine oxide photo Weight up to about 80% by Weight; initiator and an ot-hydroxyketone photo-initiator; [0064] (e) a cross-linkable, silicone acrylate, silicone [0097] (c) tetrahydrofurfuryl acrylate; methacrylate, silicone diacrylate, silicone dimethacry [0098] (d) an acrylate, methacrylate, diacrylate, late, silicone triacrylate and/ or silicone trimethacrylate; dimethacrylate, triacrylate and/or trimethacrylate [0065] (f) at least one metal salt comprising: monomer, Wherein the acrylate is other than tetrahy drofurfuryl acrylate, in an amount of about 2% by [0066] a cation selected from among Li", Na", K", Weight up to about 80% by Weight; Mg“, Ca“, A13", Zn“, Mn“, and Ag"; and [0099] (e) a cross-linkable, silicone acrylate, silicone [0067] an anion selected from among F“, Cl“, Br“, I“, methacrylate, silicone diacrylate, silicone dimethacry CO3“, C104- and N03‘; and late, silicone triacrylate and/ or silicone trimethacrylate; [0068] (g) optionally, a pigment, pigment dispersion [0100] (f) at least one metal salt comprising: a cation and/or a third photo-initiator; selected from among Li", Na", K", Mg“, Ca“, Al“, US 2008/0026662 A1 Jan. 31, 2008

Zn“, Mn“, and Ag"; and an anion selected from diacrylate, dimethacrylate, triacrylate and/ or trimethacrylate among F‘, Cl‘, Br‘, I‘, C032‘, C104 and NO3i; and monomers that are included into the compositions provided [0101] (g) optionally, a pigment, pigment dispersion are reactive only at the C=C double bond. In some embodi and/or a third photo-initiator; ments, the acrylate, methacrylate, diacrylate, dimethacry [0102] Wherein the composition is: late, triacrylate and/or trimethacrylate monomers that are [0103] (i) actinic-radiation curable; and included into the present compositions are selected from [0104] (ii) thixotropic With an apparent viscosity at among acrylate ester derivatives, methacrylate ester deriva room temperature greater than about 5000 centi tives, 2-phenoxyethyl acrylate derivatives, and cross-linking poise. acrylate derivatives. In other embodiments, the acrylate, [0105] In some embodiments, compositions provided methacrylate, diacrylate, dimethacrylate, triacrylate and/or herein include SiO2 nano-?llers at a concentration of about trimethacrylate monomers are from among acrylate ester 10% by Weight up to about 30% by Weight. In other derivatives, methacrylate ester derivatives, and cross-linking embodiments, compositions provided herein include SiO2 acrylate derivatives. In some embodiments, compositions nano-?llers at a concentration of about 10% by Weight up to provided herein include isobornyl acrylate. In other embodi about 20% by Weight. In some embodiments, compositions ments, compositions provided herein include 1,4-butanediol provided herein include SiO2 nano-?llers that have a diam dimethacrylate. In still other embodiments, compositions eter ranging from about 5 nm to about 30 nm, With an provided herein include 2-phenoxyethyl acrylate. In certain average diameter of about 20 nm. In some other embodi embodiments, compositions provided herein include 1,4 ments, compositions provided herein include SiO2 nano butanediol dimethacrylate and 2-phenoxyethyl acrylate. In ?llers that are colloidal dispersions of SiO2 in unsaturated certain other embodiments, compositions provided herein (meth-) acrylate monomers. In certain embodiments, com include propoxylated glycerol triacrylate. In some embodi positions provided herein include SiO2 nano-?ller compo ments, compositions provided herein include 1,4-butanediol sitions selected from among Nanocryl® C 350, Nanocryl® dimethacrylate, 2-phenoxyethyl acrylate and propoxylated C 130, Nanocryl® C 140, Nanocryl® C 145, Nanocryl® C glycerol triacrylate. In some other embodiments, composi 146, Nanocryl® C 150, Nanocryl® C 153, Nanocryl® C tions provided herein include methyl acrylate. In some 155, and Nanocryl® C 165. In some embodiments, compo embodiments, compositions provided herein include an sitions provided herein include Nanocryl® C 155. acrylate, methacrylate, diacrylate, dimethacrylate, triacry [0106] In certain embodiments, compositions provided late and/or trimethacrylate, selected from among tetrahydro herein include a metal salt of (I) at a concentration of about furfuryl acrylate, isobornyl acrylate, 1,4-butanediol 0.1% by Weight up to about 5% by Weight. In some dimethacrylate, 2-phenoxyethyl acrylate, propoxylated embodiments, compositions provided herein include a metal glycerol triacrylate, methacrylate, or combinations thereof. salt of (I) that comprises a cation selected from among Li+ In some embodiments, compositions provided herein and Ca2+. In other embodiments, the metal salt of (I) include an acrylate, methacrylate, diacrylate, dimethacry includes a Li+ cation. In some embodiments, the metal salt late, triacrylate and/or trimethacrylate, in addition to tetrahy of (i) includes a Ca2+ cation. In some embodiments, com drofurfuryl acrylate, selected from among isobornyl acry positions provided herein include a metal salt of (I) that late, 1,4-butanediol dimethacrylate, 2-phenoxyethyl comprises an anion selected from among Cl', Br and I“. In acrylate, propoxylated glycerol triacrylate, methacrylate, or other embodiments, the metal salt of (I) includes a Cl- anion. combinations thereof. In certain embodiments, compositions provided herein [0109] In some embodiments, compositions provided include LiCl. In other embodiments, compositions provided herein include at least one cross-linkable, silicone acrylate, herein include CaCl2. In some embodiments, compositions silicone methacrylate, silicone diacrylate, silicone include LiCl at a concentration of about 0.1% by Weight up dimethacrylate, silicone triacrylate and/or silicone tri to about 0.6% by Weight. In other embodiments, composi methacrylate. In some embodiments, the cross-linkable, tions provided herein include CaCl2 at a concentration of silicone acrylate, silicone methacrylate, silicone diacrylate, about 2% by Weight up to about 5% by Weight. silicone dimethacrylate, silicone triacrylate and/or silicone [0107] In certain of the embodiments, compositions pro trimethacrylate of (e) is a surfactant. In some embodiments, vided herein include a benZoyldiphenylphosphine oxide compositions provided include at least one cross-linkable, photo-initiator and an ot-hydroxyketone photo-initiator. In silicone acrylate, silicone methacrylate, silicone diacrylate, some embodiments, compositions provided herein include silicone dimethacrylate, silicone triacrylate and/or silicone Genocure® LTM and an ot-hydroxyketone photo-initiator. trimethacrylate selected from among TEGO® Rad 2100, In other embodiments, compositions provided herein 2200, 2250, 2300, 2500, 2600, 2650, and 2700. In some include Genocure® LTM and 1-hydroxy-cycloheXyl-phe embodiments, compositions provided herein include nyl-ketone. In other embodiments, compositions provided TEGO® Rad 2100. herein include benZophenone. In some embodiments, com [0110] In certain embodiments, compositions provided positions provided herein include Genocure® LTM and herein include: Igacure® 184. In other embodiments, compositions pro vided include Genocure® LTM, Irgacure 184® and Irga cure® 500. tetrahydro?lr?lryl acrylate 11*31% by Weight [0108] In one embodiment, compositions provided herein isobornyl acrylate 2i22% by Weight include tetrahydrofurfuryl acrylate. In some embodiments, 1,4-butanediol dimethacrylate 340% by Weight 2-phenoxyethyl acrylate 4—40% by Weight compositions provided include at least one additional acry Nanocryl ® C-155 25i50% by Weight late, methacrylate, diacrylate, dimethacrylate, triacrylate Genocure ® LTM O.5i5% by Weight and/ or trimethacrylate monomer, in addition to tetrahydro Irgacure ® 184 2*10% by Weight furfuryl. In some embodiments, the acrylate, methacrylate, US 2008/0026662 A1 Jan. 31, 2008

-continued -continued Irgacure ® 500 0.540% by Weight Genocure ® LTM 2.4% by Weight TEGO ® Rad 2100 0.01i2.0% by Weight LiCl 0.4% by Weight LiCl 0.145% by Weight [0115] In some embodiments, compositions provided [0111] In some embodiments, compositions provided herein have an apparent viscosity at room temperature herein include: greater than about 5000 centipoise. In some other embodi ments, compositions provided herein have an apparent vis cosity at room temperature greater than about 6000 centi tetrahydrofurfuryl acrylate 11*31% by Weight poise. In other embodiments, compositions provided have an isobornyl acrylate 2*22% by Weight apparent viscosity at room temperature greater than about 1,4-butanediol dimethacrylate 340% by Weight 8000 centipoise. In some embodiments, compositions pro 2-phenoxyethyl acrylate 440% by Weight Nanocryl ® C-155 2550% by Weight vided herein have an apparent viscosity at room temperature Genocure ® LTM 0.545% by Weight greater than about 10,000 centipoise. In some embodiments, Irgacure ® 184 240% by Weight compositions provided herein have an apparent viscosity at Irgacure ® 500 0.540% by Weight room temperature greater than about 15,000 centipoise. In TEGO ® Rad 2100 0.01*2.0% by Weight some embodiments, compositions provided herein have an CaCl2 0.145% by Weight apparent viscosity at room temperature greater than about 20,000 centipoise. In some embodiments, compositions pro [0112] In other embodiments, compositions provided vided herein have an apparent viscosity at room temperature herein include: greater than about 25,000 centipoise. In some embodiments, compositions provided herein have an apparent viscosity at room temperature greater than about 30,000 centipoise. In tetrahydrofurfuryl acrylate 11*31% by Weight some embodiments, compositions provided herein have an isobornyl acrylate 2*22% by Weight apparent viscosity at room temperature greater than about 1,4-butanediol dimethacrylate 340% by Weight 50,000 centipoise. In some embodiments, compositions pro 2-phenoxyethyl acrylate 440% by Weight vided herein have an apparent viscosity at room temperature Nanocryl ® C-l55 2545% by Weight Irgacure ® 184 246% by Weight greater than about 76,000 centipoise. In some embodiments, Irgacure ® 500 0.54.0% by Weight compositions provided herein have an apparent viscosity at TEGO ® Rad 2100 0.01*2.0% by Weight room temperature greater than about 100,000 centipoise. In PC 9003 142% by Weight some embodiments, compositions provided herein have an Lucerin ® TPO 0.545% by Weight Genocure ® LTM 0.545% by Weight apparent viscosity at room temperature greater than about LiCl 0.145% by Weight 300,000 centipoise. In some embodiments, compositions provided herein have an apparent viscosity at room tem perature greater than about 500,000 centipoise. In some [0113] In certain embodiments, compositions provided embodiments, compositions provided herein have an appar include: ent viscosity at room temperature greater than about 1,000, 000 centipoise. [0116] In some embodiments, compositions provided tetrahydrofurfuryl acrylate 11*31% by Weight herein are curable With sunlight. In other embodiments, isobornyl acrylate 2*22% by Weight compositions provided herein are curable With ultra-violet 1,4-butanediol dimethacrylate 340% by Weight 2-phenoxyethyl acrylate 440% by Weight (UV) radiation selected from the group consisting of UV-A Nanocryl ® C-155 2545% by Weight radiation, UV-B radiation, UV-C radiation, UV-D radiation, Irgacure ® 184 246% by Weight or combinations thereof. Irgacure ® 500 0.54.0% by Weight TEGO ® Rad 2100 0.01*2.0% by Weight [0117] In certain embodiments, provided herein is the use PC 9003 142% by Weight of a composition described herein for coating a non-metal Lucerin ® TPO 0.545% by Weight object. In some embodiments, compositions provided herein Genocure ® LTM 0.545% by Weight are impregnated into the surface of the non-metal object. In 0.145% by Weight CaCl2 some embodiments, methods provided herein further include exposing the coated non-metal object to actinic [0114] In other embodiments, compositions provided radiation and curing the coated composition. In some herein include: embodiments, the actinic radiation used is sunlight. In other embodiments, the actinic radiation used to cure the compo sitions is ultra-violet (UV) radiation selected from the group consisting of: UV-A radiation, UV-B radiation, UV-C radia tetrahydrofurfuryl acrylate 20.85% by Weight isobornyl acrylate 11.64% by Weight tion, UV-D radiation, or combinations thereof. 1,4-butanediol dimethacrylate 12.20% by Weight [0118] In some embodiments, compositions provided 2-phenoxyethyl acrylate 13.24% by Weight herein are used to coat a non-metal object selected from Nanocryl ® C-155 33.93% by Weight Irgacure ® 184 3.34% by Weight among glass substrates, polycarbonate substrates, ?ber sub Irgacure ® 500 1.95% by Weight strates, plastic substrates, ceramic substrates, cement sub TEGO ® Rad 2100 0.05% by Weight strates, brick, dryWall, stucco, electronic circuitry and com puter circuitry. US 2008/0026662 A1 Jan. 31, 2008

[0119] In certain embodiments, compositions provided [0135] (c) optionally adding a metal salt to the applied herein are used as an adhesive for UV-transparent non-metal composition of (b), Wherein the metal salt loWers the objects. In some embodiments, the UV-transparent non freeZing temperature of Water; and metal object is a glass object. In other embodiments, the [0136] (d) curing the applied composition. UV-transparent non-metal object is a polycarbonate object. [0137] In some embodiments, the composition is partially In certain embodiments, the use of a composition provided impregnated into the paper substrate and/or the herein as an adhesive for UV-transparent non-metal objects based substrate. In some embodiments, provided herein is a includes: (i) applying a composition provided herein to the paper product and/or a cellulose-based substrate produced UV-transparent non-metal object; (ii) contacting the applied by the above process. composition on the UV-transparent non-metal object of (i) [0138] In some embodiments, provided herein is a method With a second non-metal object; and (iii) curing the com of making a 100% solids, UV curable, thixotropic compo position With actinic radiation. sition, comprising: [0120] In certain embodiments, provided herein is an [0139] (a) mixing at a temperature less than 50° C.: article of manufacture that comprises: (a) a non-metal [0140] (i) SiO2 nano-?llers; object; and (b) a coating of a cured composition provided [0141] (ii) at least one photo-initiator that comprises herein. an ot-hydroxyketone; [0121] In other embodiments, provided herein is an article [0142] (iii) tetrahydrofurfuryl acrylate; of manufacture that comprises: (a) a glass object; and (b) a [0143] (iv) an acrylate, methacrylate, diacrylate, coating of a cured composition provided herein. dimethacrylate, triacrylate and/or trimethacrylate, [0122] In some embodiments, provided herein is an article Wherein the acrylate is other than tetrahydrofurfuryl of manufacture that comprises: (a) a polycarbonate object; acrylate, in an amount of about 2% by Weight up to and (b) a coating of a cured composition provided herein. about 80% by Weight; [0123] In some other embodiments, provided herein is an [0144] (v) a cross-linkable, silicone acrylate, silicone article of manufacture that comprises: (a) a ?ber object; and methacrylate, silicone diacrylate, silicone dimethacrylate, silicone triacrylate and/or silicone (b) a coating of a cured composition provided herein. trimethacrylate; [0124] In one embodiment, provided herein is a paper [0145] (vi) optionally, a pigment, pigment dispersion product and/or a cellulose-based product that comprises: (a) and/or an additional photo-initiator; a paper substrate and/or a cellulose-based substrate; and (b) a composition provided herein. [0146] (b) adding to the mixture of (a): [0147] (vii) at least one metal salt that comprises: [0125] In some embodiments, compositions provided [0148] a cation selected from among Li", Na", K", herein are impregnated into the surface of the paper sub strate and/or the cellulose-based substrate. In certain Mg2+, Ca2+, A13", Zn“, Mn“, and Ag"; and embodiments, the paper product and/or the cellulose-based [0149] an anion selected from among F“, Cl“, Br“, substrate further includes an additional metal salt in the I‘, C032‘, C104- and N03; impregnated composition, Wherein the additional metal salt [0150] (viii) optionally, Genocure® LTM; and loWers the freeZing temperature of Water. In some embodi [0151] (c) mixing the mixture for approximately 3-5 ments, the composition is cured in and/or on to the paper hours at a temperature less than 70° C. and at a speed substrate and/or on to the cellulose-based substrate. In other suf?cient to ensure an even distribution of the metal salt embodiments, the paper product and/or the cellulose-based of (vii) throughout the mixture. substrate, after exposure to Water, exhibits at least one of the [0152] In some embodiments, the method of making folloWing characteristics selected from the group consisting 100% solids, UV curable, thixotropic compositions, of: includes adding less than about 5% by Weight of oligomers. In other embodiments, less than about 2.5% by Weight of [0126] (a) retention of structural strength; oligomers are added to the compositions provided herein. In [0127] (b) retention of ink or pencil Writing; some embodiments, less than about 1% by Weight of oligo [0128] (c) retention of print; mers are added to the compositions provided herein. In other [0129] (d) retention of brightness; and embodiments, less than about 0.5% by Weight of oligomers [0130] (e) release of the additional metal salt, Which are added to the compositions provided herein. In some loWers the freeZing temperature of Water, from the other embodiments, the method of making a 100% solids, paper product. UV curable, thixotropic composition, does not include add [0131] In other embodiments, the paper product and/or the ing oligomers. cellulose-based substrate, after exposure to Water, exhibits at [0153] In some embodiments, the method of making least tWo of the aforementioned characteristics. In some 100% solids, UV curable, thixotropic compositions, embodiments, the paper product and/or the cellulose-based includes adding SiO2 nano-?llers in an amount of about 10% substrate, after exposure to Water, exhibits at least three of by Weight up to about 30% by Weight of the total Weight of the aforementioned characteristics. the composition. In other embodiments, SiO2 nano-?llers are added at a concentration of about 10% by Weight up to [0132] In another embodiment, provided herein is a pro about 20% by Weight of the total Weight of the composition. cess of making paper products and/or cellulose-based prod In certain embodiments, SiO2 nano-?llers are added, Which ucts, comprising: have a diameter ranging from about 5 nm to about 30 nm, [0133] (a) providing a paper substrate and/or a cellu With an average diameter of about 20 nm. In some embodi lose-based substrate; ments, SiO2 nano-?llers are added to the compositions as [0134] (b) applying a composition provided herein to colloidal dispersions of SiO2 in unsaturated (meth-)acrylate the paper substrate and/or the cellulose-based substrate; monomers. In other embodiments, SiO2 nano-?ller compo US 2008/0026662 A1 Jan. 31, 2008

sitions are added to the compositions provided herein, such embodiments, the cross-linkable, silicone acrylate, silicone as, for example, SiO2 nano-?ller compositions selected from methacrylate, silicone diacrylate, silicone dimethacrylate, among Nanocryl® C 350, Nanocryl® C 130, Nanocryl® C silicone triacrylate and/or silicone trimethacrylate is 140, Nanocryl® C 145, Nanocryl® C 146, Nanocryl® C TEGO® Rad 2100. 150, Nanocryl® C 153, Nanocryl® C 155, and Nanocryl® [0158] Other uses for the compositions provided herein C 165. In some embodiments, Nanocryl® C 155 is added to are described in US. patent application Ser. No. 11/234,672, the compositions provided. incorporated herein by reference. Compositions provided [0154] In other embodiments, at least one metal salt is herein, With or Without any added metal salts, can ?nd use added at a concentration of about 0.1% by Weight up to in rendering paper and ?ber based products resistant to about 5% by Weight of the total Weight of the composition. Water, see for example, US. patent application Ser. No. In some embodiments, the metal salt added to the compo 11/234,672, incorporated herein by reference. Compositions sitions provided herein include a cation selected from among provided herein, With or Without metal salts, ?nd use in Li+ and Ca2+. In certain embodiments, the metal salt added adhesion, repair, and architecture. Compositions provided to the compositions provided herein includes a Li+ cation. In herein, With or Without metal salts, ?nd use in adhesion, other embodiments, the metal salt added to the compositions repair, and architecture of non-metal substrates, to produce provided herein includes a Ca2+ cation. In some other non-metal products. embodiments, the metal salt added to the compositions provided include an anion selected from among Cl, Br“ and BRIEF DESCRIPTION OF THE DRAWINGS I‘. In some embodiments, the metal salt added to the [0159] FIG. 1 is a schematic draWing of one embodiment compositions provided include a C' anion. In some embodi of a snoW melting mat. The top and bottom sides are ments, the metal salt added to the compositions provided is indicated. LiCl. In other embodiments, the metal salt added to the [0160] FIG. 2 is a schematic draWing of one embodiment compositions provided is CaCl2. In some embodiments, of a freeZer defrosting mat. The top and bottom sides are LiCl is added at a concentration of about 0.1% by Weight up indicated. to about 0.6% by Weight of the total Weight of the compo [0161] FIG. 3 is a schematic draWing of one embodiment sition. In other embodiments, CaCl2 is added at a concen of a WindoW cover. The magnets to attach the cover to the tration of about 2% by Weight up to about 5% by Weight of body of a vehicle are indicated. the total Weight of the composition. [0162] FIG. 4 is a schematic draWing of one embodiment [0155] In certain embodiments, the method of making of shelf paper fabricated using the compositions described 100% solids, UV curable, thixotropic compositions, herein. The top and bottom sides of the shelf paper are includes adding an ot-hydroxyketone photo-initiator that indicated. comprises 1-hydroxy-cyclohexyl-phenyl-ketone. In some embodiments, the method of making 100% solids, UV INCORPORATION BY REFERENCE curable, thixotropic compositions, further includes adding [0163] All publications, patents and patent applications benZophenone. In some embodiments, the ot-hydroxyketone mentioned in this speci?cation are herein incorporated by photo-initiator that is added includes Igacure® 184. In other reference in their entirety to the same extent as if each embodiments, the ot-hydroxyketone photo-initiator(s) added individual publication, patent or patent application Was includes Irgacure 184® and Irgacure® 500. speci?cally and individually indicated to be incorporated by [0156] In some embodiments, the method of making a reference. 100% solids, UV curable, thixotropic composition, includes adding an acrylate, methacrylate, diacrylate, dimethacrylate, DETAILED DESCRIPTION OF THE triacrylate and/or trimethacrylate selected from among INVENTION isobornyl acrylate, 1,4-butanediol dimethacrylate, 2-phe noxyethyl acrylate, propoxylated glycerol triacrylate, Certain Terms methylacrylate, or combinations thereof. [0164] Unless de?ned otherWise, all technical and scien [0157] In some embodiments, the method of making a ti?c terms used herein have the same meaning as is com 100% solids, UV curable, thixotropic composition, includes monly understood by one of skill in the art to Which the adding at least one cross-linkable, silicone acrylate, silicone claimed subject matter belongs. All patents, patent applica methacrylate, silicone diacrylate, silicone dimethacrylate, tions, published applications and publications, Websites and silicone triacrylate and/or silicone trimethacrylate. In some other published materials referred to throughout the entire embodiments, at least one cross-linkable, silicone acrylate, disclosure herein, unless noted otherWise, are incorporated silicone methacrylate, silicone diacrylate, silicone by reference in their entirety. In the event that there are a dimethacrylate, silicone triacrylate and/or silicone tri plurality of de?nitions for terms herein, those in this section methacrylate, Which is a surfactant, is added to the compo prevail. Where reference is made to a URL or other such sitions provided herein. In some embodiments, the cross identi?er or address, it is understood that such identi?ers can linkable, silicone acrylate, silicone methacrylate, silicone change and particular information on the internet can come diacrylate, silicone dimethacrylate, silicone triacrylate and/ and go, but equivalent information can be found by search or silicone trimethacrylate is added at about 0.01% by ing the internet. Reference thereto evidences the availability Weight up to about 2.0% by Weight of the total Weight of the and public dissemination of such information. composition. In other embodiments, the cross-linkable, sili [0165] It is to be understood that both the foregoing cone acrylate, silicone methacrylate, silicone diacrylate, general description and the folloWing detailed description silicone dimethacrylate, silicone triacrylate and/or silicone are exemplary and explanatory only and are not restrictive of trimethacrylate is selected from among TEGO® Rad 2100, the subject matter claimed. In this application, the use of the 2200, 2250, 2300, 2500, 2600, 2650, and 2700. In other singular includes the plural unless speci?cally stated other US 2008/0026662 A1 Jan. 31, 2008

Wise. In this application, the use of “or” means “and/or” , Insulating Board, Ivory Board, Kraft Bag unless stated otherwise. Furthermore, use of the term Paper, , Kraftliner, Label Paper, , “including” as Well as other forms, such as “includes,” and Laminated Linerboard, Ledger Paper, Light Weight “included,” is not limiting. Paper, Linen Paper, Liner, Linerboard, Manifold Paper, [0166] The section headings used herein are for organiZa Manila, Mechanical Paper, Millboard, , Olf tional purposes only and are not to be construed as limiting set Paper, Packaging Paper, , Permanent the subject matter described. All documents, or portions of Paper, , Poster Paper, Board, documents, cited in the application including, but not limited Rag Paper, , Safety Paper, Sanitary Papers, to, patents, patent applications, articles, books, manuals, and Sanitary , , SiZed Paper, treatises are hereby expressly incorporated by reference in Solid , Stamp Paper, StraWboard, Tag Paper, their entirety for any purpose. Tea Bag Paper, Text Paper, Thin Paper, Tissue, Trans [0167] The term “actinic radiation” as used herein, refers parent Paper, Union Kraft, Vegetable Parchment, Vel to any radiation source Which can produce polymerization lum Paper, Wall Paper, Water-Color Paper, Waxed reactions, such as, by Way of example only, ultraviolet Paper, Wrapper, Writing Paper, YelloW Pages, and the radiation, near ultraviolet radiation, and visible light, such like; as, for example, sunlight. [0175] (b) cellulose-based products, in Which the cel [0168] As used herein, the term “photo-initiators” refers to lulose is not derived from Wood (including are products compounds that absorb ultra-violet light and use the energy made from cellulose derived from Wood and another of that light to promote the formation of a dry layer of source of cellulose); coating. Photo-initiators in the compositions provide herein, [0176] (c) various types of pulp containing products; after they absorb ultra-violet light, promote the reaction of [0177] (d) various type of shipping materials, such as, monomers With each other and thus aid in the curing but not limited to, envelopes, bags, boxes, packages, process. labels, and the like; [0169] As used herein, the term “co-photo-initiator” refers [0178] (e) various types of marker, such as, but not to a photoinitiator Which may be combined With another limited to, garden markers, underWater markers, soil photoinitiator or combination of photoinitiators. markers, and the like; [0170] As used herein, the term “cure” refers to polymer [0179] (f) various types of natural ?ber fabrics, such as, iZation, at least in part, of a coating composition. but not limited to, cotton, Wool, linen, cashmere, hemp, [0171] As used herein, the term “curable” refers to a rampie, silk, and the like; coating composition Which is able to polymeriZe at least in [0180] (g) various types of natural ?ber knits, such as, part. but not limited to, cotton, Wool, linen, hemp, rampie, [0172] As used herein, the term “curing booster” refers to silk, and the like; an agent or agents Which boost or otherWise enhance, or [0181] (h) ?ber substrates Which have non-?ber com partially enhance, the curing process. ponents, such as, but not limited to, buttons, Zippers, [0173] As used herein, the term “?ber substrates” as used pins, staples, clips, rods, and the like; and herein, refers to any object Which is, contains, or is derived [0182] (i) so-called “reneWable products,” that is prod from a natural ?ber; such objects encompass (any of the ucts made from bio-materials. folloWing classi?cations may overlap With each other): [0183] As used herein, the term “100% solids UV curable [0174] (a) various types of paper products of any basis coating” or “100% solids UV curable composition(s)” refers Weight or , bulk, caliper or thickness, to compositions/coatings that contain no added solvents or machine and cross direction, smoothness, such as, but Water Which Would require evaporation or to be driven off by not limited to, abrasive paper, absorbent paper, acid heat. As a result, there are no emissions from solvent. No free paper, acid proof paper, adhesive paper, air ?lter space is required for large ovens. No time is required for paper, air mail paper, album paper, albumin paper, evaporation or baking. Energy use is up to 80% loWer alkaline paper, aluminum foil lamination paper, ammu because heating is unnecessary. With this process, emissions nition paper, anti rust paper, antique paper, archival can be loWer still, While saving space, time and energy and paper, art paper, asphalt laminated paper, aZurelaid requiring no ?nal system for pollution control. Furthermore, paper, bag paper, or currency paper, the process described herein for applying the compositions barograph paper, base paper, , blade Wrap (i.e. coating, adhesive, sealant) to objects has the ability to ping paper, , , blueprint reclaim any over-applied, uncured solids. paper, board, , book paper, boxboard, bristol board, business form paper, , , [0184] As used herein, the term “?ller” refers to a rela , catalog paper, check or cheque paper, tively inert substance, added to modify the physical, chipboard, cigarette paper, coarse paper (also industrial mechanical, thermal, or electrical properties of a coating. paper), colfee ?lter paper, color-fast papers, construc [0185] As used herein, the term “inorganic pigment’, as tion paper, containerboard, copier paper or laser paper, used herein, refers to ingredients Which are particulate and corrugated board, or rag paper, cover substantially nonvolatile in use, and includes those ingredi paper, crepe paper, cut sheet, directory paper, document ents typically labeled as inerts, extenders, ?llers or the like paper, draWing paper, duplex board, duplex paper, in the paint and plastic trade. electrical grade paper, envelop paper, ?berboard, ?lter [0186] As used herein, the term “irradiating” refers to paper, Fine Papers, Fluorescent Paper, Folding Box exposing a surface to actinic radiation. board, Freesheet, Gasket Board, Paper, [0187] As used herein, the term “milling” refers to the GlaZed Paper, Gray Board, Green Paper, GroundWood processes of premixing, melting and grinding a poWder Papers, Handmade Paper, Index Paper, Industrial coating formulation to obtain a poWder suitable for spraying. US 2008/0026662 A1 Jan. 31, 2008

[0188] As used herein, the term “monomers” refers to example. Spectral photometric tests may also be employed substances containing single molecules that can link to to determine retention of structural strength. oligomers and to each other. Monomers, When linked to each [0200] As used herein, the term “retention of Writability of other, can form oligomers and polymers. pencil and/or ink” refers to the ability of a material to retain [0189] As used herein, the term “oligomers” refers to at least about 90% of its ability to be Written upon by any molecules containing several repeats of a single molecule. In type of pencil or any source of ink, such as a pen or printer. some cases, oligomers are made up of repeating monomer Writability depends on the absorbency of a material. units, Which are covalently linked together. Oligomers typi [0201] As used herein, the term “thixotropic” refers to cally have molecular Weights greater than 1000 daltons. compositions that shoW a decrease in apparent viscosity at [0190] As used herein, the term “organic salt” typically room temperature When shaken, stirred, agitated and/or refers to the reaction product of an organic acid and an sheared. Upon discontinuation of shaking, stirring, agitation inorganic base, such as sodium or potassium. The base can and/or shearing, thixotropic compositions revert back to the also be an organic base. Examples or organic salts include initial apparent viscosity at room temperature. Ihixotropic but are not limited to formate, acetate, propionate, pyruvate, compositions exhibit a stable form at rest but becoming ?uid oxalate, malate, tartrate, isocitrate, succinate, glutarate, When shaken, stirred, agitated and/or sheared. For example, caproate, benZoate, lactate, citrate, other carboxylates, and thixotropic paint compositions Will not run off the painter’s the like. brush, but Will still spread easily and evenly, since the [0191] As used herein, the term “polymers” refers to gel-like paint “lique?es” When brushed out. Compositions, substances containing repeating units of monomers and/or Which exhibit the opposite property, in Which shaking for a oligomers, Which are covalently linked together. time causes solidi?cation, are called rheopectic. [0202] As used herein, “apparent viscosity” refers to the [0192] As used herein, the term “polymeriZable pigment viscosity of a non-Newtonian ?uid measured under speci?c dispersions” refers to pigments attached to polymeriZable temperature and shear rate conditions. The viscosity of the Which are dispersed in a coating composition. compositions described herein are determined using a [0193] As used herein, the term “polymeriZable ” or Brook?eld viscometer DV-IILV, spindle #3 at 12 rpm, “activated resin” refers to resins Which possess reactive sample siZe 150 ml at 21° C. functional groups. [0203] As used herein, the term “vehicle” refers to the [0194] As used herein, the term “reactive functional liquid portion of solvent based formulations, and can incor group” refers to any chemical functional group that can porate both the solvent and the resin. participate in a chemical reaction With another chemical functional group thus resulting in a covalent chemical bond. Compositions [0195] As used herein, the term “pigment” refers to a [0204] Compositions provided herein, are useful for coat compound Which is insoluble or partially soluble, and is ing non-metal substrates, as adhesives, and as sealants. used to impart color. Compositions provided herein are 100% solids UV curable [0196] As used herein, the term “retention of brightness” coatings, and thus ?nd use, for example, in a variety of refers to the ability of a material to retain at least about 90% architectural applications. Use of the compositions provided of its brightness. Retention of brightness prevents discol herein as coating materials, as adhesives, as sealing com oration, such as darkening or yelloWing, of a material. positions, are curable With actinic radiation to produce novel Representative tests for determining retention of brightness coatings, adhesive ?lms and seals. Compositions provided include spectrophotometric tests, such as optical absorption herein are useful in combination With a variety of consumer, test for brightness (Wavelength:457 nm) and/or luminance scienti?c, and industrial products, Which Would bene?t from (Wavelength:555 nm), for example. a cured coating of a composition provided herein. [0197] As used herein, the term “retention of ink or pencil [0205] Compositions provided herein are useful for ren Writing” refers to the ability of ink or pencil Writing to be at dering non-metal objects resistant to Water. In some embodi least about 90% retained on a material. Retention of ink or ments, provided herein are non-metal objects that include a pencil Writing prevents bleeding, fading, and/ or streaking on cured coating of a composition provided, Wherein the cured a material. Representative tests for determining retention of coated non-metal object exhibits at least one of the folloW ink or pencil Writing include spectrophotometric tests, such ing characteristics after exposure to Water for at least one as the Ink Elimination (IE) test and the Effective Residual day: Ink Concentration (ERIC) test, for example. [0206] (a) retention of structural integrity; [0198] As used herein, the term “retention of print” refers [0207] (b) retention of structural strength; to the ability of print to be at least about 90% retained on a [0208] (c) retention of ink, paint or pencil Writing; material. Representative prints include various ink prints, [0209] (d) retention of print; such as labels, logos, and the like. Retention of print [0210] (e) retention of brightness; prevents bleeding, fading, and/or streaking on a material. [0211] (f) resistance to mold, algae, mildeW, bacterial, Representative tests for determining retention of print and/or fungal groWth. include various spectral photometric tests. [0212] In some embodiments, non-metal objects that are [0199] As used herein, the term “retention of structural coated With a composition provided herein exhibit at least strengt ” refers to the ability of a material to retain at least tWo of the above-mentioned characteristics, at least three of about 90% of its physical and structural integrity, strength, the above-mentioned characteristics, at least four of the or durability. Retention of structural strength prevents tear above-mentioned characteristics, at least ?ve of the above ing, ripping, or breaks. Representative mechanical tests for mentioned characteristics, or all of the above-mentioned determining retention of structural strength include manual characteristics. Also provided, are non-metal objects that inspection, folding endurance, and tensile strength, for include a cured coat of a composition provided herein that US 2008/0026662 A1 Jan. 31, 2008

exhibit at least one of the above-mentioned characteristics, 25,000 centipoise; or greater than about 30,000 centipoise at at least tWo of the above-mentioned characteristics, at least room temperature. In some embodiments, compositions four of the above-mentioned characteristics, or all of the provided herein have an apparent viscosity at room tem above-mentioned characteristics, after exposure to Water for perature greater than about 50,000 centipoise. In some at least 2 days, at least 3 days, at least 7 days, and at least embodiments, compositions provided herein have an appar 10 days. In some embodiments, exposure to Water includes ent viscosity at room temperature greater than about 76,000 soaking, misting, spraying, seeping, or combinations centipoise. In some embodiments, compositions provided thereof. Compositions provided herein are useful for Water herein have an apparent viscosity at room temperature proo?ng non-metal objects. In some embodiments, non greater than about 100,000 centipoise. In some embodi metal objects that include a cured coating of a composition ments, compositions provided herein have an apparent vis provided herein retain desirable aesthetic, performance and cosity at room temperature greater than about 300,000 durability properties, When exposed to moisture and/or centipoise. In some embodiments, compositions provided Water, including exposure for prolonged periods of time. herein have an apparent viscosity at room temperature [0213] Compositions provided herein are 100% solids, greater than about 500,000 centipoise. In some embodi UV-curable compositions that ?nd use as, for example, ments, compositions provided herein have an apparent vis coatings, adhesives, sealants and any other architectural use. cosity at room temperature greater than about 1,000,000 Compositions provided herein do not contain any Water or centipoise. organic solvent, Which must be removed before complete [0220] Compositions provided herein, are thixotropic With curing is achieved. Therefore, the compositions provided an apparent resting-state viscosity suitable for providing a herein are less haZardous to the environment, and are stable, non-?oWing composition, Which becomes ?uid When economical because they require less space, less energy and agitated, shaken, mixed and/or sheared, thus alloWing the less time. Compositions provided herein can be used in composition to be applied to the surfaces of materials as combination With thermally sensitive substrates. coats, as adhesives and/or as sealants. The compositions [0214] Coating materials, folloWing their application to provided herein, after they have been agitated, shaken, materials, are required to exhibit very good stability in order mixed and/or sheared, and then applied to the surfaces of that they permit the production of comparatively thick non-metal substrates, revert back to the resting-state viscos coating ?lms and/or coats Without exhibiting the extremely ity, producing non-?oWing coats that can then be cured With disruptive running, especially on vertical surfaces and/or actinic radiation to produce non-metal products that include substrates. The viscosity of the coating materials, such as, a cured composition provided herein. for example, the compositions provided herein, must not be [0221] In one embodiment, the compositions provided so high that problems arise during application and the herein include: applied coating ?lms and/ or coats are no longer able to ?oW [0222] (a) SiO2 nano-?llers; out e?fectively. Coats, such as, for example, clearcoats, [0223] (b) a benZoyldiphenylphosphine oxide photo should posses favorable properties such as gloss, transpar initiator and an ot-hydroxyketone photoinitiator; ency and clarity, scratch resistance, Weathering stability, and [0224] (c) tetrahydrofurfuryl acrylate; yelloW stability. The aforementioned properties of coating [0225] (d) an acrylate, methacrylate, diacrylate, materials are desirable for adhesive ?lms and seals. dimethacrylate, triacrylate and/or trimethacrylate, [0215] Thixotropic compositions provided herein have Wherein the acrylate is other than tetrahydrofurfuryl very good application properties, very good stability, and acrylate and is present at a concentration of about 2% very good ?oW, Which produces coats upon UV curing, by Weight up to about 80% by Weight; Which have favorable properties such as gloss, transparency [0226] (e) a cross-linkable, silicone acrylate, silicone and clarity, scratch resistance, Weathering stability, and methacrylate, silicone diacrylate, silicone dimethacry yelloWing stability. late, silicone triacrylate and/ or silicone trimethacrylate, [0216] Provided herein are composition that are: [0227] (f) at least one metal salt including: [0217] (a) thixotropic With an apparent viscosity greater [0228] a cation selected from among Li", Na", K", than about 5000 centipoise at room temperature; and Mg2+, Ca2+, A13: Zn2+, Mn2+, Ti2+’ Ti3+’ Ti4+’ CD2+’ [0218] (b) are actinic radiation curable. C03", Sc3+ and Ag"; [0219] Compositions provided herein are thixotropic, [0229] an anion selected from among F‘, Cl‘, Br‘, I‘, exhibiting a stable form at rest but becoming ?uid When C032, C104“ and N03“; and agitated, shaken, mixed and/or sheared. The agitated, [0230] (g) optionally, a pigment, pigment dispersion shaken, mixed and/or sheared ?uid compositions revert back and/or a third photo-initiator. to their stable form at rest in the absence of agitation, [0231] In one embodiment, compositions provided herein shaking, mixing and/or shearing after an amount of time. In are applied to glass objects, polycarbonate objects, ceramic certain embodiments, compositions provided herein are objects and non-metal objects. In one embodiment, compo thixotropic, With an apparent viscosity greater than about sitions provided herein are applied to ?ber substrates to 5000 centipoise at room temperature. In some embodiments, produce ?ber products having desirable properties. In compositions provided herein are thixotropic, With an appar another embodiment, the compositions provided herein, are ent viscosity greater than about 6000 centipoise; about 7000 applied to glass objects, polycarbonate objects, ceramic centipoise; about 8000 centipoise; about 9000 centipoise; objects, non-metal objects and ?ber objects and exposed to about 10,000 centipoise; about 11,000 centipoise; about actinic radiation in order to cure the applied compositions. 12,000 centipoise; about 13,000 centipoise; about 14,000 [0232] In one embodiment, compositions provided herein centipoise; about 15,000 centipoise; about 16,000 centi include SiO2 nano-?llers in an amount of about 10% by poise; about 17,000 centipoise; about 18,000 centipoise; Weight up to about 30% by Weight of the total Weight of the about 19,000 centipoise; about 20,000 centipoise; about composition (Wt/Wt). In certain embodiments, compositions US 2008/0026662 A1 Jan. 31, 2008

provided herein include at least one benZoyldiphenylphos embodiments, compositions provided herein can be used as phine oxide photo-initiator in an amount of 0.1% by Weight sealants. In certain embodiments, compositions provided up to about 2% by Weight. In a further embodiment, the herein are used to coat computer circuitry or electronic compositions provided herein include Genocure® LTM in circuitry, in order to render the circuitry resistant to Water an amount of 0.5% by Weight up to about 5% by Weight. In and/or to preserve the existing print on the circuitry and/or certain embodiments, compositions provided herein include preserve thermal conductivity Without compromising clar at least one ot-hydroxyketone photo-initiator in an amount of ity. about 1% by Weight up to about 6% by Weight. In some [0235] Coating ?exibility may be an important character embodiments, the compositions provided herein include istic for compositions herein When applied to objects Which benZophenone in an amount ranging from about 0.5% by ?ex, distort, or otherWise change shape, such as, but not Weight up to about 2% by Weight. In further or alternative limited to, fabrics and cloths. Coating ?exibility alloWs the embodiments, compositions provided herein include tet composition to ?ex or distort Without cracking When the rahydrofurfuryl acrylate in an amount of 10% by Weight up object ?exes, distorts or changes shape; Whereas coating to about 30% by Weight. In some embodiments, the com adhesion properties alloWs the coating to remain attached to position provided include at least one acrylate, methacrylate, the object When the object ?exes, distorts or changes shape. diacrylate, dimethacrylate, tiacrylate and/ or trimethacrylate, Certain embodiments of the compositions described herein Wherein the acrylate is other than tetrahydrofurfuryl acry may be used to obtain and optimiZe desirable properties. late, in an amount of about 2% by Weight up to about 80% by Weight. In another embodiment, the compositions pro Nano-Fillers vided herein include a cross-linkable, silicone acrylate, [0236] In some embodiments, compositions provided silicone methacrylate, silicone diacrylate, silicone herein include silicon dioxide (SiO2) nano-?llers (nano dimethacrylate, silicone triacrylate and/or silicone tri silicon dioxide). Silicon dioxide nano-?llers having a methacrylate in an amount of about 0.01% by Weight up to nanometer siZe, including by Way of example, silicon diox about 2.0% by Weight. In certain embodiments, the compo ide particles With a diameter less than about 200 nm, and by sitions provided herein include a pigment or pigment dis Way of further example, a diameter ranging from about 5 nm persion in an amount of about 1% by Weight up to about 12% to about 40 nm, can be incorporated into compositions by Weight. provided herein. Addition of silicon dioxide nano-?llers to [0233] Compositions described herein can be applied to a the compositions provided herein may impart improved variety of substrates, including, for example, glass sub toughness, hardness and abrasion and scratch resistance. strates, polycarbonate substrates, ceramic substrates, non Other properties and features obtained When incorporating metal substrates and ?ber substrates to produce glass prod silicon dioxide nano-?llers into compositions provided ucts, polycarbonate products, ceramic products, non-metal herein can include: it acts as a barrier effect against gases, products and ?ber products. Compositions described herein Water vapor and solvents; it has increased Weathering resis can be applied to a variety of substrates, including, for tance and inhibited thermal aging; it exhibits reduced cure example, glass substrates, polycarbonate substrates, ceramic shrinkage and heat of reaction, reduced thermal expansion substrates, non-metal substrates and ?ber substrates, and and internal stresses, increased tear resistance, fracture then cured With actinic radiation to produce glass products, toughness and modulus, has improved adhesion to a large polycarbonate products, ceramic substrates, non-metal prod number of inorganic substrates (e.g., glass, aluminum), has ucts and ?ber products. Compositions described herein are improved dirt resistance against inorganic impurities (e.g., curable by actinic radiation, such as, for example, various soot) by a more hydrophilic surface, and has improvements sources of visible radiation, near visible radiation, ultra to other desired properties such as: thermal stability, stain violet (UV) radiation, and combinations thereof. UV radia resistance, heat conductivity, dielectric properties. tion can be selected from the group consisting of UV-A [0237] Compositions that incorporate silicon dioxide radiation, UV-B radiation, UV-C radiation, UV-D radiation, nano-?llers ?nd use in abrasion resistant coating applica or combinations thereof. Compositions described herein are tions requiring superior optical transparency such as eye curable by sunlight. glasses; ?ne polishing applications, including semiconduc [0234] Coating the surfaces of various objects With solvent tors; and nanocomposite applications, including improved based coatings can be problematic due to environmental thermal management. In addition, incorporation of silicon issues stemming from evaporation of the volatile solvent. dioxide nano-?llers can give rise to compositions With Also, such solvent based coatings can require thermal cur improved impact resistance, abrasion resistance and scratch ing, resulting in the need for curing ovens and the associated resistance. energy expenditure to operate them. Compositions provided [0238] Silicon dioxide nano-?llers are commercially herein are cured by actinic radiation. Compositions provided available as compositions that include silicon dioxide nano herein do not require thermal curing. In one embodiment, particles in acrylate monomers, methacrylate monomers, compositions provided herein are cured by actinic radiation, acrylate oligomers and/or methacrylate oligomers. Repre such as, for example, sunlight. In some embodiments, com sentative silicon dioxide nano-?ller compositions include positions provided herein are applied to non-metal objects, those sold under the name Nanocryl® C by Hanse Chemie such as, for example, glass, polycarbonate, ceramic, brick, (Geesthacht, Germany). Nancryl® C products are colloidal cement, stucco, dryWall, ?ber substrates, Wood, paper, or dispersions of up to 50% by Weight of amorphous silica in any other suitable non-metal material on the outside of a a Wide range of conventional unsaturated (meth-)acrylate building or home, and then cured With sunlight. Composi monomers and oligomers. The dispersed phase consists of tions provided herein are curable by sunlight in a matter of surface-modi?ed, spherically shaped SiO2 nanoparticles hours in cold temperatures, such as, for example, Winter having a diameter ranging from about 5 nm up to about 30 Weather, Without any need for thermal curing. In other nm, With an average diameter of about 20 nm. In some US 2008/0026662 A1 Jan. 31, 2008

embodiments, the silicon dioxide nano-?llers in the compo temperature, barrier properties, UV resistance, abrasion and sitions provided herein include those such as, for example, scratch resistance, and conductivity. The incorporation of Nanocryl® C 350, Nanocryl® C 130, Nanocryl® C 140, certain nano-?llers, such as, for example, nano-silicon, can Nanocryl® C 145, Nanocryl® C 146, Nanocryl® C 150, provide favorable long-term coating Without signi?cantly Nanocryl® C 153, Nanocryl® C 155, and Nanocryl® C 165. e?‘ecting optical clarity, gloss, color or physical properties. In certain embodiments, the compositions provided herein These improved properties may be in large part due to the include Nanocryl® C 155. small siZe and large surface area of the nanoscale ?llers. [0239] The average particle siZe of nano-?llers in the compositions described herein include, by Way of example, Photo-Initiators less than about 200 nm, and by Way of further example, With an average particle siZe about 5 nm up to about 50 nm. In [0244] In certain embodiments, compositions provided some embodiments, nano-?ller particles in the compositions herein include at least one photo-initiator. In certain embodi provided herein have an average diameter of about 10 mm, ments, compositions provided herein include at least tWo about 20 mm, about 30 nm, or about 40 nm. In another photo-initiators. In some embodiments, compositions pro embodiment, the nano-?ller particles have a diameter about vided herein include at least three photo-initiators. In some 1 nm up to about 60 mm, such as, for example, a diameter embodiments, compositions provided herein include at least of about 5 nm up to about 30 nm. four photo-initiators. [0240] Nano-?llers are present in the compositions pro [0245] Compositions provided herein include at least one vided herein in an amount ranging from about 10% by photo-initiator. In some embodiments, compositions pro Weight up to about 30% by Weight (Wt/Wt), such as from vided herein include a combination of photo-initiators. In about 10% by Weight up to about 25% by Weight, from about some embodiments, compositions provided herein include at 10% by Weight up to about 20% by Weight, or from about least one photo-initiator selected from among phosphine 10% by Weight up to about 18% by Weight. In some oxide photo-initiator(s), ot-hydroxyketone photo-initiator(s), embodiments, the compositions provided herein include benZophenone or substituted benZophenones, tertiary amine nano-?llers in an amount from about 13% by Weight up to photo-initiator(s), thioxanthone(s), Norish Type I photo about 18% by Weight. In some embodiments, the nano-?llers initator(s) Norish Type II photo-initator(s), and/or transition are SiO2 nano-?llers. metal based photo-initiator(s). [0241] Nano-?ller compositions, such as, for example, [0246] In some embodiments, compositions provided Nanocryl® C compositions, are present in the compositions herein include at least one benZoyldiphenylphosphine oxide provided herein in an amount ranging from about 20% by photo-initiator and at least one ot-hydroxyketone photo Weight up to about 60% by Weight, such as from about 25% initiator. In some embodiments, compositions provided by Weight up to about 55% by Weight, from about 25% by herein include at least one benZoyldiphenylphosphine oxide Weight up to about 50% by Weight, from about 25% by photo-initiator, at least one ot-hydroxyketone photo-initiator Weight up to about 40% by Weight, or from about 25% by and benZophenone. In some embodiments, compositions Weight up to about 35% by Weight. In some embodiments, provided herein include Genocure® LTM and an ot-hydrox the present compositions include a Nanocryl® C composi yketone photo-initiator. In some other embodiments, com tion from about 30% by Weight up to about 36% by Weight. positions provided herein include Genocure® LTM, an In some embodiments, the compositions provided herein ot-hydroxyketone photo-initiator, and benZophenone. In cer include a Nanocryl® C composition selected from among tain embodiments, compositions provided herein include at Nanocryl® C 350, Nanocryl® C 130, Nanocryl® C 140, least one phosphine oxide photo-initiator, such as, for Nanocryl® C 145, Nanocryl® C 146, Nanocryl® C 150, example, mono-acylphosphine oxides and/or bis-acylphos Nanocryl® C 153, Nanocryl® C 155, Nanocryl® C 165. In phine oxides. certain embodiments, compositions provided herein include [0247] Generally, photo-initiators are added to initiate Nanocryl® C 155. In some embodiments, the compositions rapid polymeriZation of monomers in the composition upon provided herein include a combination of Nanocryl® C exposure to a source of actinic radiation, such as, for compositions. In some embodiments, compositions pro example, ultraviolet light. The photo-initiator(s) can be vided herein include at least one Nanocryl® C composition. matched to the spectral properties of the UV source, such as, In certain embodiments, compositions provided herein for example, medium pressure mercury arc lights Which include one Nanocryl® C composition. produce intense UV-C (200-280 nm) radiation, doped mer [0242] The addition of ?llers imparts certain rheological cury discharge lamps Which produce LV-A (315-400 nm) properties to the composition, such as, for example, viscos radiation, or UV-B (280-315 nm) radiation depending on the ity; hoWever, the addition of nanoscale ?llers (nano-?llers) dopant, or combination of lamp types. Depending on the imparts dramatically different effects on the coating photo-initiator or combination of photo-initiators in the mechanical properties in comparison to micron-scale ?llers. compositions, varying UV source(s) may be employed. Thus, the mechanical properties of the composition can be Photo-initiators provided herein can initiate rapid polymer manipulated by varying the amount of micron-siZed ?llers iZation of monomers upon exposure to a source of actinic and nano-?llers. In some embodiments, compositions pro radiation. In some embodiments, photo-initiators provided vided herein include a combination of micron-siZed ?llers herein can initiate rapid polymerization of monomers upon and nano-?llers. In certain embodiments, compositions pro exposure to a source of actinic radiation, such as, for vided herein include nano-?llers. In certain embodiments, example, sunlight. compositions provided herein include a combination of [0248] Any suitable type of photo-initiator(s) may be used nano-?llers. in the compositions, including those categoriZed as free [0243] Improved properties attributable to nano-?llers radicals. The photo-initiator(s) may be in liquid or solid include improved tensile strength, modulus, heat distortion form. Furthermore, combinations of photo-initiators may be US 2008/0026662 A1 Jan. 31, 2008

used Which encompass different spectral properties of the ot-hydroxyketone photo-initiator, such as, for example, UV sources used to initiate polymerization. 1-hydroxy-cyclohexyl-phenyl-ketone. In certain embodi [0249] In certain embodiments, the photo-initiators ments, compositions provided herein include at least one present in the compositions provided herein are selected ot-hydroxyketone photo-initiator. In some embodiments, from among phosphine oxide type photo-initiators, ot-hy compositions provided herein include at least one ot-hydrox droxyketone photo-initiators, benZophenone photo-initia yketone photo-initiator and benZophenone. In certain tors, and combinations thereof. In certain embodiments, the embodiments, compositions provided herein include at least photo-initiator(s) present in the compositions provided one phosphine oxide photo-initiator and at least one ot-hy herein may be selected from among GENOCURE® LTM droxyketone photo-initiator, such as, for example, 1-hy (Rahn USA Corporation, 1005 North Commons Drive, droxy-cyclohexyl-phenyl-ketone. In some embodiments, Aurora, Ill.), diphenyl(2,4,6-trimethylbenZoyl)phosphine compositions provided herein include at least three initia oxide, benZophenone, ESACURE® KTO, IRGACURE® tors, such as, for example, Genocure® LTM, at least one 184, IRGACURE® 500, DARACUR® 1173, Lucirin® ot-hydroxyketone photo-initiator, such as, for example, TPO, 1-hydroxycyclohexyl phenyl ketone, (2-hydroxy-2 1-hydroxy-cyclohexyl-phenyl-ketone, and benZophenone. methyl-1 -phenyl-propan-1 -one), (2,4,6-trimethylbenZophe In certain embodiments, compositions provided herein none), 4-methylbenZophenone, phosphine oxide type pho include at least three photo-initiators, such as, for example, toinitiators, oligo(2-hydroxy-2-methyl-1-(4-(1 -methylvinyl) at least one phosphine oxide photo-initiator, at least one phenyl)propanone), and combinations thereof. In another ot-hydroxyketone photo-initiator, such as, for example, embodiment, compositions provided herein include photo 1-hydroxy-cyclohexyl-phenyl-ketone, and benZophenone. initiator(s) selected from among phosphine oxide type pho In certain embodiments, the compositions provided herein toinitiators, GENOCURE® LTM, diphenyl-(2,4,6-trimeth include benZophenone. In another or alternative embodi ylbenZoyl)phosphine oxide, benZophenone, ment, compositions provided herein include at least one l-hydroxycyclohexyl phenyl ketone, IRGACURE® 184, benZoyl diaryl phosphine photo-initiator, such as, for IRGACURE® 500, 2-hydroxy-2-methyl-1-phenyl-propan example, trimethylbenZoyldiphenylphosphine oxide. In 1-one (DAROCUR® 1173 from Ciba Specialty Chemicals some embodiments, the compositions provided herein 540 White Plains Road, TarrytoWn, N.Y., U.S.A.)), (2,4,6 include at least one ot-hydroxyketone photo-initiator, such trimethylbenZophenone), 4-methylbenZophenone, ESA as, for example, 1-hydroxy-cyclohexyl-phenyl-ketone. CURE® KTO 46 (Lamber‘ti S.p.A., Gallarate (VA), Italy), [0252] In certain embodiments, compositions provided oli go (2 -hydroxy-2-methyl-1 -(4-(1-methylvinyl)phenyl)pro herein include a combination of photo-initiators. In some panone), amine acrylates, thioxanthones, benZyl methyl embodiments, compositions provided herein include ketal, and mixtures thereof. In a further embodiment, com GENOCURE® LTM, IRGACURE® 184 and IRGA positions provided herein include photo-initiators selected CURE® 500. In another embodiment, compositions pro from among 2-hydroxy-2-methyl-1 -phenyl-propan-1 -one vided herein include GENOCURE® LTM, IRGACURE® (DAROCUR® 1173), phosphine oxide type photoinitiators, 184, IRGACURE® 500, and Lucirin® TPO. GENOCURE® LTM, diphenyl-(2,4,6-trimethylbenZoyl) [0253] Depending on the required ?lm thickness of the phosphine oxide, IRGACURE® 184, IRGACURE® 500, compositions provided herein, the amount of photo-initiator IRGACURE® 819, IRGACURE® 1700 (Ciba Specialty (s) may be increased or adjusted accordingly. Generally, for Chemicals 540 White Plains Road, TarrytoWn, N.Y., US. thinner ?lms, larger amounts of photo-initiator(s) are A.), amine acrylates, thioxanthones, benZyl methyl ketal, required. In some embodiments, faster curing is achieved by and mixtures thereof. using a combination of photo-initiators. Compositions pro [0250] Other photo-initiators, Which are suitable for use in vided herein include photo-initiators in an amount ranging the compositions provided herein, include, but are not from about 0.5% by Weight up to about 10% by Weight. In limited to, 1 -phenyl-2-hydroxy-2 -methyl- 1 -propanone, some embodiments, compositions provided herein include oli go {2 -hydroxy-2-methyl -1 ,4 -(methylvinyl)phenylpro - photo-initiator(s) in an amount ranging from about 1% by panone) }, 2-hydroxy-2-methyl-1-phenylpropan-1-one, bis Weight up to about 9% by Weight, from about 3% by Weight (2,6-dimethoxybenZoyl)-2,4,4-trimethylpentyl phosphine up to about 8% by Weight, from about 4% by Weight up to oxide, 1-hydroxycyclohexyl phenyl ketone and benZophe about 8% by Weight, or from about 5% by Weight up to about none, as Well as mixtures thereof. Still other useful photo 8% by Weight. initiators for use in the compositions provided herein [0254] In certain embodiments, compositions provided include, for example, bis(n5-cyclopentadienyl)-bis-(2,6-di herein include a combination of photo-initiators, Wherein ?uoro-3 -(1H-pyrol-1 -yl)phenyl)titanium (IRGACURE® each photo-initiator is present in an amount ranging from 784) and 2-benZyl-2-dimethylamino-1-(4-morpholinophe about 0.01% by Weight up to about 5% by Weight, such as nyl)-1-butanone (IRGACURE® 369). While, still other use from about 0.1% by Weight up to about 4% by Weight or ful photoiniators include, for example, 2-methyl-1,4-(meth from about 0.5% by Weight up to about 4% by Weight. In ylthio)-2-morpholinopropan-1-one, 4-(2 -hydroxy) -phenyl some embodiments, compositions provided herein include 2-hydroxy-2-(methylpropyl)ketone, 1 -hydroxy GENOCURE® LTM in an amount ranging from about 0.5% cyclohexylphenyl ketone, benZophenone, by Weight up to about 4% by Weight, such as from about 1% (cyclopentadienyl)(1-methylethyl)benZene-iron hexa?uoro by Weight up to about 3% by Weight, such as about 1% by phosphate, (2,2-dimethoxy-2-phenyl-1 -acetophen-one), Weight, about 1.5% by Weight, about 2% by Weight, about (2,4,6-trimethylbenZoyl-diphenyl phosphine oxide), benZoic 2.5% by Weight or about 3% by Weight. In some embodi acid, 4-(dimethylamino)-ethyl ether, as Well as mixtures ments, compositions provided herein include IRGACURE® thereof. 184 in an amount ranging from about 2% by Weight up to [0251] In certain embodiments, compositions provided about 6% by Weight, such as about 2% by Weight, about herein include at least Genocure® LTM and at least one 2.5% by Weight, about 3% by Weight, about 3.5% by Weight, US 2008/0026662 A1 Jan. 31, 2008

about 4% by Weight, about 4.5% by Weight, about 5% by the C=C double bond of the acrylate and/or methacrylate Weight, or about 6% by Weight. In some embodiments, moiety of the monomer molecule. In certain embodiments, compositions provided herein include IRGACURE® 500 in the present compositions include a combination of mono an amount ranging from about 0.5% by Weight up to about mers. Upon exposure to a source of actinic radiation, such as 4% by Weight, such as about 0.5% by Weight, about 1% by ultraviolet light, and in the presence of a photo-initiator, Weight, about 1.5% by Weight, about 2% by Weight, about monomers in the compositions provided herein are rapidly 2.5% by Weight, about 3% by Weight, about 3.5% by Weight polymeriZed to form polymers and/or oligomers. or about 4% by Weight. [0259] The mechanical properties of the present compo [0255] In some embodiments, compositions provided sitions, such as hardness, loW shrinkage, high glass transi herein include trimethyl-benZoyldiphenylphosphine oxide tion temperatures (Tg), desirable elasticity, and ?exibility in an amount of about 0.01% by Weight up to about 1% by depend upon the type of monomers that are included the Weight, such as about 0.1%, about 0.2%, about 0.4%, about compositions. By Way of example only, polyester acrylates 0.6%, about 0.8% or 1% by Weight. In some embodiments, combine good abrasion resistance With toughness, Whereas compositions provided herein include an ot-hydroxyketone urethane acrylates and polyether acrylates can provide ?ex photo-initiator in an amount ranging from about 2% by ibility, elasticity and hardness. Thus, the composition Weight up to about 6% by Weight, such as about 2% by described herein combine monomers Which impart various Weight, about 2.5% by Weight, about 3% by Weight, about properties to obtain compositions that are hard, abrasion 3.5% by Weight, about 4% by Weight, about 4.5% by Weight, resistant, scratch resistant, and impact resistant. about 5% by Weight, or about 6% by Weight. In some [0260] In certain embodiments, compositions described embodiments, compositions provided herein include ben herein include at least one reactive monomer that produces Zophenone in an amount ranging from about 0.25% by polymers through the formation of free radicals When Weight up to about 2% by Weight, such as about 0.25% by exposed to a source of actinic radiation, such as ultraviolet Weight, about 0.5% by Weight, about 0.75% by Weight, light. In certain embodiments, compositions described about 1% by Weight, about 1.25% by Weight, about 1.5% by herein include a combination of reactive monomers that Weight, about 1.75% by Weight or about 2% by Weight. produces polymers through the formation of free radicals [0256] In some embodiments, compositions provided When exposed to a source of actinic radiation, such as, for herein include a pigment, or pigment dispersion in combi example, ultraviolet light. In some embodiments, the reac nation With a phosphine oxide photo-initiator, such as, for tive monomers provided herein produce polymers through example, a benZoyldiarylphosphine oxide photo-initiator. the formation of free radicals When exposed to a source of Although the presence of pigments and/or pigment disper actinic radiation through the aid of photo-initiators. sions can absorb actinic radiation both in the UV and visible [0261] Reactive monomers suitable for incorporation into light regions and reduce the effectiveness of some types of the present compositions exhibit at least one of the folloWing photo-initiators, phosphine oxide type photo-initiators are properties: (a) high UV reactivity; (b) loW shrinkage; (c) effective in pigmented composition, including, by Way of good balance of hardness and ?exibility; (d) high UV example only, black and colored UV-curable coating mate stability after polymerization; (e) good viscosity reduction; rials. Phosphine oxides also ?nd use as photo-initiators for and/or (f) loW toxicity and irritancy. White coatings. In some embodiments, compositions pro [0262] Monomers provided herein are classi?ed as mono vided herein include a pigment and/or pigment dispersion functional monomers or multi-functional monomers, and at least one trimethylbenZoyl-diphenylphosphine oxide depending upon the number of acrylate and/ or methacrylate photo-initiator, such as, for example, phosphine oxide units in the monomer(s). In some embodiments, the com photo-initiators sold under the tradename GENOCURE® positions provided include reactive monomers, such as, for LTM or Lucirin® TPO. example, acrylates, methacrylates, diacrylates, dimethacry [0257] In certain embodiments, compositions provided lates, triacrylates and/or trimethacrylates. In certain embodi herein include at least one benZoyldiaryl phosphine oxide ments, acrylates, methacrylates, diacrylates, dimethacry photo-initiator in an amount ranging from about 0.01% by lates, triacrylates and/ or trimethacrylates that are Weight up to about 5%, from about 0.01% by Weight up to incorporated into the present compositions are reactive at the about 4% by Weight, from about 0.05% by Weight up to C=C double bond of the (meth-)acrylate moiety of the about 3% by Weight, from about 0.1% by Weight up to about monomer. In certain embodiments, acrylates, methacrylates, 2% by Weight, from about 0.5% by Weight up to about 3% diacrylates, dimethacrylates, triacrylates and/ or trimethacry by Weight, or from about 1% by Weight up to about 3% by lates that are incorporated into the present compositions are Weight. In certain embodiments, compositions provided reactive at the C=C double bond of the (meth-)acrylate herein include at least one benZoyldiarylphosphine oxide moiety of the monomer and are not reactive at other sites of photo-initiator in an amount of about 0.01% by Weight, about 0.05% by Weight, about 0.1% by Weight, 0.5% by the monomer(s). Weight, about 1% by Weight, about 2% by Weight, about 3% [0263] In certain embodiments, compositions provided by Weight, or about 4% by Weight. herein include a combination of monomers. In certain embodiments, compositions provided herein include at least Monomers one monomer that functions as a diluent, Which aids in the solubiliZation of other components of the compositions [0258] In some embodiments, compositions provided and/or aids in providing favorable viscosity characteristics herein include at least one mono-functional monomer. In to the compositions provided herein. In some embodiments, some embodiments, compositions provided herein include compositions provided herein include a monomer selected acrylate and/or methacrylate type monomers. In certain from among isobomyl acrylate, isodecyl acrylate, trimethy embodiments, compositions provided herein include acry lolpropane triacrylate (TMPTA), di-trimethylolpropane tria late and/or methacrylate type monomers that are reactive at crylate (Di-TMPTA), propoxylated TMPTA (PO6-TMPTA), US 2008/0026662 A1 Jan. 31, 2008

and combinations thereof. In certain embodiments, compo 30% by Weight or from about 10% by Weight up to about sitions provided herein include isobornyl acrylate. 25% by Weight. Each monomer is present in the composi [0264] In some embodiments, compositions provided tions provided herein in an amount of about 5%, about 10%, herein include at least one monomer selected from among about 20%, about 30%, about 40%, about 50%, about 60%, 2-phenoxyethyl acrylate, isobomyl acrylate, acrylate ester about 70%, or about 80% by Weight (Wt/Wt). derivatives, methacrylate ester derivatives, tetrahydrofurfu [0269] In certain embodiments, compositions provided ryl acrylate, trimethylolpropane triacrylate, 2-phenoxyethyl herein include tetrahydrofurfuryl acrylate. In certain acrylate esters, and cross-linking agents, such as, but not embodiments, compositions provided herein include tet limited to, propoxylated glyceryl triacrylate, tripropylene rahydrofurfuryl acrylate in an amount ranging from about glycol diacrylate, and mixtures thereof. In some embodi 10% by Weight up to about 30% by Weight, such as from ments, compositions provided herein include non-aromatic about 10% by Weight up to about 25% by Weight or from monomers. In some embodiments, compositions provided about 15% by Weight up to about 25% by Weight. In certain herein include at least one aromatic monomer. embodiments, compositions provided herein include tet [0265] In some embodiments, the present compositions rahydrofurfuryl acrylate in an amount of about 10%, about include a combination of monomers. In some embodiments, 15%, about 20%, about 25% or about 30% by Weight. In compositions provided herein include at least one monomer some embodiments, compositions provided herein include selected from among 2-phenoxyethyl acrylate, 1,4-butane tetrahydrofurfuryl in an amount of about 16% by Weight up diol dimethacrylate, tetrahydrofurfuryl acrylate, propoxyl to about 23% by Weight. glyceroltriacrylate, methylacrylate, and combinations [0270] In some embodiments, compositions provided thereof. herein include 2-phenoxyethyl acrylate in an amount rang [0266] Compositions provided herein include monomers ing from about 4% by Weight up to about 40% by Weight, selected from among acrylates, methacrylates, diacrylates, such as from about 4% by Weight up to about 30% by dimethacrylates, triacrylates and trimethacrylates. In some Weight, about 4% by Weight up to about 25% by Weight, or embodiments, compositions provided herein include tet from about 5% by Weight up to about 15% by Weight. rahydrofurfuryl and at least one additional monomer [0271] In some embodiments, compositions provided selected from among acrylates, methacrylates, diacrylates, herein include 1,4-butanediol dimethacrylate in an amount dimethacrylates, triacrylates and trimethacrylates. In certain ranging from about 4% by Weight up to about 40% by embodiments, compositions provided herein include tet Weight, such as from about 4% by Weight up to about 30% rahydrofurfuryl, isobomyl acrylate and at least one addi by Weight, about 4% by Weight up to about 25% by Weight, tional monomer selected from among acrylates, methacry or from about 5% by Weight up to about 15% by Weight. In lates, diacrylates, dimethacrylates, triacrylates and certain embodiments, compositions provided herein include trimethacrylates. In some embodiments, compositions pro 1,4-butanediol dimethacrylate in an amount of about 5%, vided include tetrahydrofurfuryl acrylate, isobomyl acrylate, about 10%, about 15% or about 20% by Weight. 1,4-butanediol dimethacrylate, and at least one additional [0272] In certain embodiments, compositions provided monomer selected from among acrylates, methacrylates, herein include isobornyl acrylate in an amount ranging from diacrylates, dimethacrylates, triacrylates and trimethacry about 2% by Weight up to about 20% by Weight, such as lates. In some embodiments, compositions provided herein from about 5% by Weight up to about 18% by Weight, about include tetrahydrofurfuryl acrylate, isobornyl acrylate, 1,4 7% by Weight up to about 15% Wt/Wt, or from about 9% by butanediol dimethacrylate, 2-phenoxyethyl acrylate, and at Weight up to about 12% by Weight. least one additional monomer selected from among acry [0273] In some embodiments, compositions provided lates, methacrylates, diacrylates, dimethacrylates, triacry herein include propoxylglycerol triacrylate in an amount lates and trimethacrylates. In some embodiments, composi tions provided herein include tetrahydrofurfuryl acrylate, ranging from about 2% by Weight up to about 30% by isobornyl acrylate, 1,4-butanediol dimethacrylate, 2-phe Weight, such as from about 5% by Weight up to about 25% noxyethyl acrylate, propoxyl glyceroltriacrylate, and at least by Weight, or from about 10% by Weight up to about 20% by Weight. In some embodiments, compositions provided one additional monomer selected from among acrylates, methacrylates, diacrylates, dimethacrylates, triacrylates and herein include propoxylglycerol triacrylate in an amount of trimethacrylates. about 5%, about 8%, about 12%, about 14%, about 16%, about 18%, about 20%, about 22%, about 24%, about 26% [0267] In certain embodiments, monomer(s) are present in or about 28% by Weight. the compositions in an amount ranging from about 2% by Weight up to about 90% by Weight (Wt/Wt), such as from Cross-Linkable, Silicone Monomers about 10% by Weight up to about 85% by Weight, from about 15% by Weight up to about 85% by Weight, from about 20% [0274] Compositions provided herein include at least one by Weight up to about 80% by Weight, from about 25% by cross-linkable, silicone acrylate, silicone methacrylate, sili Weight up to about 80% by Weight, from about 30% by cone diacrylate, silicone dimethacrylate, silicone triacrylate Weight up to about 80% by Weight, from about 40% by and/or silicone trimethacrylate. In certain embodiments, the Weight up to about 75% by Weight or from about 50% by cross-linkable, silicone acrylate, silicone methacrylate, sili Weight up to about 75% by Weight. cone diacrylate, silicone dimethacrylate, silicone triacrylate [0268] In some embodiments, compositions provided and/or silicone trimethacrylate is a surfactant. Cross-link herein include a mixture of monomers, Wherein each mono able, silicone acrylates, silicone methacrylates, silicone dia mer is present in an amount from about 2% by Weight up to crylates, silicone dimethacrylates, silicone triacrylates and/ about 50% by Weight, such as from about 5% by Weight up or silicone trimethacrylates are employed to impart desirable to about 40% by Weight, from about 5% by Weight up to properties to compositions, such as improved slip, scratch about 35% by Weight, from about 5% by Weight up to about resistance, ?oW, levelling, release, and defoaming. US 2008/0026662 A1 Jan. 31, 2008

[0275] Cross-linkable, silicone acrylates, silicone meth include a loW concentration of metal salts. In some embodi acrylates, silicone diacrylates, silicone dimethacrylates, sili ments, a catalytic amount of metal salt(s) is/are included into cone triacrylates and/or silicone trimethacrylates are com the compositions provided herein, such as, for example, less mercially available, such as those manufactured under the than about 10% by Weight, less than about 5% by Weight, name TEGO® Rad by Degussa AG (Essen, Germany) and less than about 2% by Weight, less than about 1% by Weight include TEGO® Rad 2100, 2200, 2250, 2300, 2500, 2600, or less than about 0.5% by Weight of the total Weight of the 2650, and 2700. In some embodiments, compositions pro composition. vided herein include at least one cross-linkable, silicone [0280] In certain embodiments, compositions provided acrylate, silicone methacrylate, silicone diacrylate, silicone herein include at least one metal salt that aids in the dimethacrylate, silicone triacrylate and/or silicone tri polymeriZation of the monomers that are present. In some methacrylate selected from among TEGO® Rad 2100, 2200, embodiments, compositions provided herein include at least 2250, 2300, 2500, 2600, 2650, and 2700. In certain embodi one metal salt that partially polymeriZes the composition to ments, compositions provided include at least TEGO® Rad produce a thixotropic composition. In certain embodiments, 2100. the presence of at least one metal salt in the compositions [0276] In some embodiments, compositions provided provided herein produces a thixotropic, non-sticky compo herein include at least one cross-linkable, silicone acrylate, sition. Absence of the metal salt(s) from the compositions silicone methacrylate, silicone diacrylate, silicone provided herein produces compositions that are less viscous dimethacrylate, silicone triacrylate and/or silicone tri than identical compositions that include at least one metal methacrylate in an amount ranging from about 0.01% by salt. Weight up to about 2.0% by Weight, such as about 0.01%, [0281] In one embodiment, compositions provided herein about 0.02%, about 0.03%, about 0.04%, about 0.05%, include at least one metal salt that is ioniZable. In another about 0.06%, about 0.07%, about 0.08%, about 0.09%, embodiment, compositions provided herein include at least about 0.1%, about 0.5%, about 0.8%, about 1.0%, about one metal salt With a cation that has a small positive charge. 1.2%, about 1.4%, about 1.6%, about 1.8, or about 2.0% by In certain embodiments, compositions provided herein Weight. include at least one metal salt With a cation that has a small, [0277] Other surfactants that may be used in the compo localiZed positive charge. In some embodiments, composi sitions provided herein include, but are not limited to, tions provided herein include anhydrous metal salts. Metal polymers such as, for example, polystyrene, polypropylene, salts that are included in the compositions provided herein polyesters, styrene-methacrylic acid type copolymers, sty can be obtained from a variety of commercial sources. rene-acrylic acid type copolymers, polytetra?uoroethylene, [0282] In certain embodiments, compositions provided polychlorotri?uoroethylene, polyethylenetetra?uoroethyl herein include at least one alkali metal salt. In certain ene type copolymers, polyaspartic acid, polyglutamic acid, embodiments, compositions provided herein include at least and polyglutamic acid-y-methyl esters; and modi?ers such one alkaline metal salt. In certain embodiments, composi as silane coupling agents and alcohols. Additional surfac tions provided herein include at least one metal salt selected tants that may be employed in the compositions provided from among alkali metal salts and alkaline metal salts. In herein include ole?ns, such as, for example, polyethylene, certain embodiments, compositions provided herein include polypropylene, polybutadiene, and the like; vinyls, such as, at least one transition metal salt. In certain embodiments, for example, polyvinylchloride, polyvinylesters, and poly compositions provided herein include at least one metal salt styrene; acrylic homopolymers and copolymers; phenolics; that includes a cation selected from among Li", Na", K", amino resins; alkyds, epoxys, siloxanes, nylons, polyure Mg2+, Ca2+, A13: Zn2+, Mn2+, Ti2+’ Ti3+’ Ti4+’ CD2+’ CD3+’ thanes, phenoxys, polycarbonates, polysulfones, polyesters Sc3+ and Ag". In another embodiment, compositions pro (optionally chlorinated), polyethers, acetals, polyimides, and vided herein include at least one metal salt that includes a polyoxyethylenes. Further exemplary surfactants include cation selected from among Li", Na", K", Mg“, and Ca2+. cross-linked as Well as non-crosslinked acrylates that are In another embodiment, compositions provided herein compatible With UV curing compositions, such as crosslink included at least one metal salt that includes a cation selected able silicone acrylate. from among Li+ and Ca2+. In some embodiments, compo [0278] In certain embodiments, compositions provided sitions provided include at least one metal salt that includes herein include surfactant(s) in an amount ranging from about a Li+ cation. In another embodiment, compositions provided 0.01% by Weight up to about 2.0% by Weight, such as about include a metal salt that includes a Ca2+ cation. 0.01%, about 0.02%, about 0.03%, about 0.04%, about [0283] In one embodiment, the compositions provided 0.05%, about 0.06%, about 0.07%, about 0.08%, about herein include at least one metal salt that includes an anion 0.09%, about 0.1%, about 0.5%, about 0.8%, about 1.0%, selected from among F“, Cr, Br“, I“, C032“, C104“ and N03. about 1.2%, about 1.4%, about 1.6%, about 1.8, or about In another embodiment, compositions provided herein 2.0% by Weight. include at least one metal salt that includes an anion selected from among Cl‘, Br‘, I‘, and C032. In yet another embodi Metal Salts ment, the compositions provided herein include at least one [0279] In some embodiments, compositions provided metal salt that includes an anion selected from among Cl‘, herein include at least one metal salt. Metal salts, When Br“, and I“. In still another embodiment, the compositions incorporated into the compositions provided herein, confer provided herein include at least one metal salt that includes a variety of properties to the compositions. Metal salts, When a Cl- anion. incorporated into the compositions provided herein, aid in [0284] In certain embodiments, composition provided the curing process, aid in the polymerization process, create herein include at least one metal salt selected from among a thixotropic composition, and/or provided other desirable LiCl, NaCl, KCl, MgCl2, CaCl2, AgCl, ZnCl2, LiBr, LiI, properties and/or qualities. Compositions provided herein NaBr, NaI, KBr, KI, MgBr2, MgI2, CaBr2, CaI2, AgBr, AgI,