Halogen-free flame retardant (METH)acrylate resins

Abstract

The present invention relates to halogen-free flame retardant (meth) acrylate resin compositions, their method of preparation and their use, particularly in applications requiring high strength and rigidity, along with flame retardant capabilities. The compositions include one or more nitrogen-containing (meth) acrylate reactive component (s); one or more phosphorous-containing (meth) acrylate reactive component (s); and at least ' one curing system.

Description

HALOGEN-FREE FLAME RETARDANT (METH)ACRYLATE RESINS BACKGROUNDField

[0001] The present invention relates to halogen-free flame retardant (meth)acrylate resin compositions, their method of preparation and their use, particularly in applications requiring high strength and rigidity, along with flame retardant capabilities. The compositions include one or more nitrogen- containing (meth)acrylate reactive component(s); one or more phosphorous-containing (meth)acrylate reactive component(s); and at least one curing system.Brief Description Related Technology

[0002] Flame tetardant materials are known to prevent or slow down the propagation of fire after ignition. In the past, flame retardant capabilities of a polymer matrix have been achieved using the addition of long-standing flame retardants, commonly inorganic fillers. However, with respect to certain applications such as Resin Transfer Molding (RTM), fillers are not desired in resin where low viscosity, transparency and processability are needed.

[0003] While epoxies have been used heretofore in commercial applications because they possess certain flame retardant capabilities, they are often too rigid and may have unfavorably high viscosities for many commercial applications. Epoxies have also been combined with silicone resins as two part systems, but such compositions have been shown to have poor tensile and tear strengths and high temperature curing requirements.Additionally, polyurethane compositions have also been used as the matrix in flame retardant compositions, but moisture sensitivity and foaming during curing and softer durometercharacteristics have made them less desirable. Further, phenolics have also been used because they possess certain flame-retardant capabilities, but they possess certain environmentally compromising characteristics.

[0004] Fillers, such as ammonium phosphates or fumed silicas, have also been used to augment flame-retardancy. Fumed silicas tend to drastically increase the viscosity of the system, while ammonium phosphate particles tend to not disperse well in systems leading to phase separation.

[0005] Halogenated flame retardants have been widely used in the field, functioning by reacting with free radicals in the flame. However, due to environmental concerns of toxic gases released by halogenated products, halogen-free flame retardants are being increasingly scrutinized governmental environmental authorities and their use has become an issue in the field.

[0006] Therefore, it would be advantageous to find a halogen- free (meth)acrylate resin composition which possesses excellent mechanical properties such as low viscosity, transparency, processability, and which exhibits high flame retardant capabilities as evidenced by fast self-extinguishing times and low residues and, which also does not possess environmentally hazardous characteristics.SUMMARY

[0007] The present invention solves the problems of the industry by producing halogen-free flame-retardant acrylate resins without requiring fillers or halogen compounds, but instead providing compositions that are relatively low viscosity, flowable compositions which exhibit high flame retardant capabilities as evidenced by low residues and fast self-extinguishing times.

[0008] One advantageous aspect of the present invention provides a flame-retardant resin composition including: a) one or more nitrogen-containing (meth)acrylate reactive component(s), b) one or more phosphorous-containing (meth)acrylate reactive component(s), and c) at least one cure system, wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing (meth)acrylate reactive component(s) is from about 1 to 1 to about 10 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of total composition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.

[0009] Another advantageous aspect of the present invention provides a flame-retardant reaction product including the reaction of: a) one or more nitrogen-containing (meth)acrylate reactive component(s), b) one or more phosphorous-containing (meth)acrylate reactive component(s), and c) at least one cure system, wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing (meth)acrylate reactive component(s) is from about 1 to 1 to about 10 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of total composition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.

[0010] Yet another advantageous aspect of the present invention provides a flame-retardant composition including: a) a nitrogen-containing (meth)acrylate reactive component selected from the group consisting of tris(2-hydroxyethyl)isocyanurate triacrylate (SR368), 4-acryloylmorpholine (ACMO), and combinations thereof, b) a phosphorous-containing (meth)acrylate reactive component selected from the group consisting of bis hydroxyethyl (meth)acrylate (HEMA) phosphate, 2- hydroxyethyl (meth)acrylate phosphate (Harcryl 1228), and combinations thereof, c) at least one cure system, and wherein a ratio of nitrogen-containing (meth)acrylate reactive component to phosphorous-containing (meth)acrylate reactive component is from about 1 to 1 to about 3 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 20% to about 30% by weight of total composition, and a flame extinguishing time of about 0 seconds to about 10 seconds when burned for 30 seconds.

[0011] Still a further advantageous aspect of the present invention provides a flame-retardant resin composition including: a) one or more nitrogen-containing (meth)acrylate reactive component(s), b) one or more phosphorous-containing non-(meth)acrylate additive component(s), and c) at least one cure system, wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing non- (meth)acrylate additive component(s)is from about 1 to 1 to about 10 to 1, andwherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of total composition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.

[0012] Yet another advantageous aspect of the present invention provides a method of making a flame-retardant composition including the steps of: a) combining one or more nitrogen-containing (meth)acrylate reactive component(s), with b) one or more phosphorous-containing (meth)acrylate reactive component(s), c) at least one cure system, and wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing (meth)acrylate reactive component(s) is from about 1 to 1 to about 10 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of total composition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.DETAILED DESCRIPTIONDefinitions

[0013] The term "and / or" means each of the listed components may be present together, or may be present in the alternative to each other.

[0014] The term "conventionally-sized" means having a particle size that is not in the nano-sized range as defined herein. For example, conventionally-sized may refer to, but is not limited to, a range of about 10 micrometers to about 50 micrometers or greater.

[0015] The term "cured" means the reaction converting the fluid mix to the solid bond or coating of this invention.

[0016] The term "(meth)acryl" as used herein indicates acryl, methacryl or any combination thereof. Similarly, the term "(meth)acryloxy" indicates acryloxy, methacryloxy or any combination thereof; the term "(meth)acrylic acid" indicates acrylic acid, methacrylic acid or any combination thereof; the term "(meth)acrylate" indicates acrylate, methacrylate or any combination thereof; and the term "(meth)acrylamide" indicates acrylamide, methacrylamide or any combination thereof. The number of the (meth)acryl groups in the (meth)acrylate usable in the present invention is not particularly limited and can be one or more.

[0017] The term "nano-sized" means having a particle size in the range of about 1 nm to about 100 nm.

[0018] The term "non-(meth)acrylate" means a compound which does not possess (meth)acrylate functionality.

[0019] The term "oligomer" as used herein refers to relatively low molecular weight polymeric compounds which include at least two monomer units linked to each other. Desirably the oligomer includes from 2 to 1000 monomer units linked to each other, and more desirably 2 to 300 monomer units, or 2 to 200 monomer units or 2 to 100 monomer units, or 2 to 50 monomer units or 2 to 40 monomer units, or 2 to 30 monomer units, or 2 to 20 monomer units, or 2 to 10 monomer units, or 1 to 5 monomer units linked to each other.

[0020] The term "redox" means a chemical reaction in which one component is oxidized (losing electrons) and the other is reduced (gaining electrons).

[0021] The term "RT" means a room temperature of about 20°C to about 25°C.Nitrogen-Containing (Meth)acrylates

[0022] The compositions of the present invention include one or more nitrogen-containing (meth)acrylate reactive component(s).

[0023] In one advantageous aspect of the present invention, the nitrogen-containing (meth)acrylate reactive component(s) may be a cyclic structure.

[0024] In another advantageous aspect of the present invention, the nitrogen-containing (meth)acrylate reactive component(s) may be a non-cyclic structure.

[0025] Among the useful nitrogen-containing (meth)acrylate reactive component(s) of the present invention include tris(2- hydroxyethyl)isocyanurate triacrylate (SR368), 4- acryloylmorpholine (ACMO), N,N-dimethylacrylamide (NNDMA), vinylimidazole triallyl-isocyanurate (TAICROS), N- vinylpyrrolidone (NVP), and combinations thereof.

[0026] In one particularly advantageous aspect of the present invention, the nitrogen-containing (meth)acrylate reactive component(s) desirably may be tris(2-hydroxyethyl)isocyanurate triacrylate (SR368).

[0027] In some advantageous aspects of the present invention, other monomers may be included, such as acryloyl morpholine, N- vinyl pyrrolidone and vinylimidazole. Such monomers may be used as diluents to adjust the viscosity suitable for the intended applications.

[0028] The nitrogen-containing (meth)acrylate reactive component(s) may be present in the present invention in amounts of about 20% to about 80%, about 25% to about 80%, about 30% to about 80%, about 35% to about 80%, about 40% to about 80%, about 45% to about 80%, about 50% to about 80%, about 55% to about 80%, about 60% to about 80%, about 65% to about 80%, about 70%to about 80%, and about 75% to about 80%, all percentages weight by total composition.

[0029] The nitrogen-containing (meth)acrylate reactive component(s) may also be present in the present invention in amounts of about 20% to about 70%, about 25% to about 70%, about 30% to about 70%, about 35% to about 70%, about 40% to about 70%, about 45% to about 70%, about 50% to about 70%, about 55% to about 70%, about 60% to about 70%, and about 65% to about 70%, all percentages weight by total composition.

[0030] The nitrogen-containing (meth)acrylate reactive component(s) may also be present in the present invention in amounts of about 20% to about 60%, about 25% to about 60%, about 30% to about 60%, about 35% to about 60%, about 40% to about 60%, about 45% to about 60%, about 50% to about 60%, and about 55% to about 60%, all percentages weight by total composition.

[0031] The nitrogen-containing (meth)acrylate reactive component(s) may also be present in the present invention in amounts of about 20% to about 50%, about 25% to about 50%, about 30% to about 50%, about 35% to about 50%, about 40% to about 50%, and about 45% to about 50%, all percentages weight by total composition.

[0032] The nitrogen-containing (meth)acrylate reactive component(s) may also be present in the present invention in amounts of about 20% to about 40%, about 25% to about 40%, about 30% to about 40%, and about 35% to about 40%, all percentages weight by total composition.

[0033] The nitrogen-containing (meth)acrylate reactive component (s) may also be present in the present invention in amounts of about 20% to about 30%, and about 25% to about 30%, all percentages weight by total composition.Nano-silica Fillers

[0034] In another advantageous aspect of the present invention, nano-silica fillers may optionally be included. Such fillers are nano-sized particles which may be dispersed in a (meth)acrylate based material in a weigh percent of the base material of about 50% or less.

[0035] In one advantageous aspect of the present invention, suitable nano-fillers may have a diameter ranging from about 5 nm to about 30 nm, with an average diameter of about 20 nm. In other advantageous aspects of the present invention, suitable nano-fillers may include SiO nano-fillers that are colloidal dispersions of SiO in unsaturated (meth-) acrylate monomers. Suitable nano-silica particle dispersion in (meth)acrylate resins include, but are not limited to, Evonik GNBH Essen Germany Nanocryl products such as, Nanocryl(R) C 350, Nanocryl(R) C 130, Nanocryl(R) C 140, Nanocryl(R) C 145, Nanocryl(R) C 146, Nanocryl(R) C 150, Nanocryl(R) C 153, Nanocryl(R) C 155, and Nanocryl(R) C 165, hexanedioldiacrylate (HDDA) nanosilica particles, trimethylolpropane triacrylate (TMPTA) with 50% nanosilica, hydroxyethyl methacrylate (HEMA) with 50% nanosilica, and combinations thereof.

[0036] In one advantageous aspect of the present invention, the nano-silica filler may be present in amounts of about 1% to about 30%, about 2% to about 30%, about 3% to about 30%, about4% to about 30%, about 5% to about 30%, about 6% to about 30%, about 7% to about 30%, about 8% to about 30%, about 9% to about30%, about 10% to about 30%, about 11% to about 30%, about 12% to about 30%, about 13% to about 30%, about 14% to about 30%, about 15% to about 30%, about 16% to about 30%, about 17% to about 30%, about 18% to about 30%, about 19% to about 30%, about 20% to about 30%, about 21% to about 30%, about 22% to about 30%, about 23% to about 30%, about 24% to about 30%, about 25%to about 30%, about 26% to about 30%, about 27% to about 30%, about 28% to about 30%, and about 29% to about 30%, all percentages by weight of the total composition.Phosphorous-Containing (Meth)acrylates

[0037] The compositions of the present invention include one or more phosphorous-containing (meth)acrylate reactive component(s).

[0038] One advantageous aspect of the present invention includes the phosphorous-containing (meth)acrylate reactive component(s) selected from bis HEMA phosphate, phosphorus- containing di-functional acrylated oligomers (RAYLOK 1722), 2- hydroxyethyl-methacrylate-phosphate (VISIOMER HEMA-P100), 2- hydroxyethyl methacrylate phosphate (Harcryl 1228), and combinations thereof.

[0039] In advantageous aspects of the present invention, the amount of phosphorous present in the phosphorous-containing (meth)acrylate reactive component(s) may be about 5% to about 20%, about 6% to about 20%, about 7% to about 20%, about 8% to about 20%, about 9% to about 20%, about 10% to about 20%, about 11% to about 20%, about 12% to about 20%, about 13% to about 20%, about 14% to about 20%, about 15% to about 20%, about 16% to about 20%, about 17% to about 20%, about 18% to about 20%, and about 19% to about 20%, all percentages by weight of the phosphorous-containing (meth)acrylate.

[0040] In some advantageous aspects of the present invention, the amount of phosphorous present in the phosphorous-containing (meth)acrylate reactive component(s) may be about 5% to about 15%, about 6% to about 15%, about 7% to about 15%, about 8% to about 15%, about 9% to about 15%, about 10% to about 15%, about 11% to about 15%, about 12% to about 15%, about 13% to about15%, and about 14% to about 15%, all percentages by weight of the phosphorous-containing (meth)acrylate.

[0041] In some advantageous aspects of the present invention, the amount of phosphorous present in the phosphorous-containing (meth)acrylate reactive component(s) may be about 5% to about 10%, about 6% to about 10%, about 7% to about 10%, and about 8% to about 10%, about 9% to about 10%, all percentages by weight of the phosphorous-containing (meth)acrylate.

[0042] In some advantageous aspects of the present invention, the amount of phosphorous present in the phosphorous-containing (meth)acrylate reactive component(s) is desirably about 5% to about 20% percentage by weight of the phosphorous-containing (meth)acrylate.

[0043] In some advantageous aspects the present invention, the phosphorous-containing (meth)acrylate reactive component(s) may be present in amounts of about 10% to about 50%, about 15% to about 50%, about 20% to about 50%, about 25% to about 50%, about 30% to about 50%, about 35% to about 50%, about 40% to about 50%, and about 45% to about 50%, all percentages weight by total composition.

[0044] In another advantageous aspect of the present invention, the phosphorous-containing (meth)acrylate reactive component(s) may also be present in amounts of about 10% to about 40%, about 15% to about 40%, about 20% to about 40%, about 25% to about 40%, about 30% to about 40%, and about 35% to about 40%, all percentages weight by total composition.

[0045] In another advantageous aspect of the present invention, the phosphorous-containing (meth)acrylate reactive component(s) may also be present in amounts of about 10% to about 30%, about 15% to about 30%, about 20% to about 30%, and about 25% to about 30%, all percentages weight by total composition.

[0046] In still another advantageous aspect of the present invention, the phosphorous-containing (meth)acrylate reactive component(s) may also be present in amounts of about 10% to about 20%, and 15% to about 20%, all percentages weight by total composition.

[0047] In a further advantageous aspect of the present invention, the phosphorous-containing (meth)acrylate reactive component(s) may also be present in amounts of about 10% to about 50% percentage weight by total composition.

[0048] In advantageous aspects of the present invention, the ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing (meth)acrylate reactive component(s) may be from about 1 to 1 to about 2 to 1, or about1 to 1 to about 3 to 1, or about 1 to 1 to about 4 to 1, or about 1 to 1 to about 5 to 1, or about 1 to 1 to about 6 to 1, or about 1 to 1 to about 7 to 1, or about 1 to 1 to about 8 to1, or about 1 to 1 to about 9 to 1, or about 1 to 1 to about 10 to 1.Curing Systems

[0049] The compositions of the present invention may be formulated using different curing systems respectively or two or more of the systems may be used together.

[0050] In one advantageous aspect of the present invention, the composition may be cured using a photo-cure system with the addition of photoinitiators. The composition may be photo-cured by UV / Visible light at RT or may be heat cured, depending on the application.

[0051] In a further advantageous aspect of the present invention, the curing system may be selected from a photo-curingsystem, a heat curing system, a chemical curing system, and combinations thereof.

[0052] Photoinitiators useful in the present invention include, but are not limited to, UV initiators. In one advantageous aspect of the present invention, the photoinitiator may be a polymeric structure to which is attached at least one chromophore that is excited by radiation in the UV light.

[0053] A variety of UV initiators may be employed in any of the inventive compositions. UV initiators are generally effective in the 200 to 400 nm range, and particularly in the portion of the spectrum that borders on the invisible light and the visible portion just beyond this, such as greater than 200 nm to about 390 nm.

[0054] Among the useful initiators that will respond to UV radiation to initiate and induce curing of the (meth)aery1 functionalized curable component include, but are not limited to, benzophenone and substituted benzophenones, acetophenone and substituted acetophenones, benzoin and its alkyl esters, xanthone and substituted xanthones, phosphine oxides, diethoxyacetophenone, benzoin methylether, benzoin ethylether, benzoin isopropylether, diethoxyxanthone, chlorothioxanthone, N- methyldiethanol-amine-benzophenone, 2-hydroxy-2methyl—1—phenyl- propan—1—one, 2-benzyl-2-(dimethylamino)—1—[4—(4— morpholinyl)phenyl]-1-butanone and mixtures thereof. Examples of such UV initiators include initiators available commercially from IGM Resins under the "OMNIRAD" (formerly "IRGACURE") and "DAROCUR" trade names, specifically "OMNIRAD" 184 (1- hydroxycyclohexylphenylketone), 907 (2-methyl—1—[4- (methylthio)phenyl]-2-morpholinopropan—1—one), 369 (2-benzyl-2 - N,Ndimethylamino-1-(4-morpholinophenyl)-1-butanone), 500(the combination of 1-hydroxcyclohexyl phenylketone and benzophenone), 651(2,2-dimethoxy-2-phenylacetophenone), 1700(the combination of bis(2,6-dimethoxybenzoyl-2,4,4- trimethylpentyl) phosphine oxide and 2-hydroxy-2-methyl—1— phenyl-propan—1—one), 819 [bis(2,4,6,6-trimethylbenzoylphenyl phosphine oxide], ethyl(2,4,6-trimethylbenzoyl)-phenyl phosphinate (Omnirad TPO-L) "DAROCUR" 1173 (2-hydroxy-2-methyl- 1-phenyl—1—propane) 4265 (the combination of 2,4,6- trimethylbenzoyldiphenyl-phosphineoxide and 2-hydroxy-2-methyl- lphenyl-propan-1-one), and 2,4,6- trimethylbenzoyldiphenylphosphine oxide (commercially available as LUCIRIN TPO from BASF Corp.), and combinations thereof.

[0055] In a further particularly useful aspect of the present invention, the photoinitiator desirably is ethyl(2,4,6- trimethylbenzoyl)-phenyl phosphinate (Omnirad TPO-L).

[0056] Photoinitiators may be present in the present in the invention in amounts of about 0.5% to about 5.0%, about 1.0% to about 5.0%, about 1.5% to about 5.0%, about 2.0% to about 5.0%, about 2.5% to about 5.0%, about 3.0% to about 5.0%, about 3.5% to about 5.0%, about 4.0% to about 5.0%, and about 4.5% to about 5.0%, all percentages by weight of the total composition.

[0057] Redox cure is also suitable where generally redox initiators including a metal reducing agent and a peroxide are used. Non-limiting examples of useful peroxides include benzoyl peroxide (Luperox A75), dicumyl peroxide, tert-butyl hydroperoxide, tert-butylperoxybenzoate, dibenzoyl peroxide, peroxyacetic acid, and combinations thereof.

[0058] Catalysts are optional. Nonetheless, that skilled artisan may choose to incorporate catalysts into the inventive compositions in amounts useful for promoting cure.

[0059] Among the useful catalysts include transition metal catalysts, such as a copper salt or chelate. The copper may be a copper carboxylate, copper naphthenate, copper acetate, copper octoate, copper laurate, copper benzoate, fatty acid salts ofcopper, copper formate, copper metal, copper acetyl acetonate, 2,4-pentanedione copper complex, any other analogous copper compounds, alloys, amalgams, and copper derivatives known to those skilled in the art.

[0060] As used herein the term "metal catalyst" means a metal-containing compound or complex that contributes to determining the position of the atom transfer equilibrium and dynamics of exchange between dormant and active species. Thus, the metal catalyst employed should desirably be a good electron donor. Suitable metal catalysts include, for example, Cu(0), Cu2S, Cu2Te, Cu2Se, Mn, Ni, Pt, Fe, R, V, and combinations thereof. Similarly, other suitable metal catalysts, including, for example, Au, Ag, Hg, Rh, Co, Ir, Os, Re, Mn, Cr, Mo, W, Nb, Ta, Zn, and compounds including one or more of the foregoing. Desirably, the metal catalyst is Cu(0), Cu2S, Cu2Te, Cu2Se, or a combination thereof.

[0061] For example, useful amounts of catalysts in the present invention include about 1% to about 10%, about 2% to about 10%, about 3% to about 10%, about 4% to about 10%, about 5% to about 10%, about 6% to about 10%, about 7% to about 10%, about 8% to about 10%, and about 9% to about 10%, all percentages weight by total composition.

[0062] Heat curing systems are also suitable, in which case thermal initiators may be included. Useful examples of thermal initiators include compounds such as 2,2'- azobis(isobutyronitrile) (AIBN), benzoyl peroxide, cumene hydroperoxide, 2,2'-azobis[2-(2-imidazolin-2-yl)-propane] dihydrochloride, di-tert-butyl peroxide, dicumyl peroxide, dicyanamide, cyclohexyl tosylate, and combinations thereof.

[0063] In a particularly desirable aspect of the present invention, the thermal initiator may be benzoyl peroxide (Luperox A75).

[0064] In an aspect of the present invention, the thermal initiators may be present in amounts of about 0.5% to about 5.0%, about 1.0% to about 5.0%, about 1.5% to about 5.0%, about 2.0% to about 5.0%, about 2.5% to about 5.0%, about 3.0% to about 5.0%, about 3.5% to about 5.0%, about 4.0% to about 5.0%, and about 4.5% to about 5.0%, all percentages by weight of the total composition.

[0065] In a further advantageous aspect of the present invention, the redox initiators, including a metal catalyst and a peroxide may be present in amounts of about 0.5% to about 5.0%, about 1.0% to about 5.0%, about 1.5% to about 5.0%, about 2.0% to about 5.0%, about 2.5% to about 5.0%, about 3.0% to about 5.0%, about 3.5% to about 5.0%, about 4.0% to about 5.0%, and about 4.5% to about 5.0%, all percentages by weight of the total composition.

[0066] In a further advantageous aspect of the invention, suitable redox initiators include, but are not limited to, dihydrophenylpyridine (PDHP), cumene hydroperoxide (CHP), N- benzoylthiourea (BTU) and copper naphthenate (8% Cu NAP All), and combinations thereof.Nitrogen-Containing AdditivesWithout (Meth)Acrylate Functionality

[0067] In another aspect of the present invention, nitrogen- containing, flame-retardant compounds which do not have (meth)acrylate functionality may be optionally included.

[0068] Useful nitrogen-containing non-(meth)acrylates compounds include, but are not limited to melamine, melamine derivatives such as melamine cyanurate, melamine polyphosphate,melamine borate, melamine ammonium, guanidine and its salts, N- alkoxy hindered amines,azoalkanes, phosphazenes, phospham, and combinations thereof.

[0069] In an advantageous aspect of the present invention, nitrogen-containing non-(meth)acrylate may be present in amounts of about 1% to about 30%, about 5% to about 30%, about 10% to about 30%, about 15% to about 30%, about 20% to about 30%, and about 25% to about 30%, all percentages by weight of the total composition.Phosphorous-Containing Additives Without (Meth)Acrylate Functionality

[0070] In another advantageous aspect of the present invention, phosphorous-containing, flame-retardant compounds which do not contain (meth)acrylate functionality may be optionally included. For example, such compounds may include, without limitation, phosphorous-based oligomers having phenolic hydroxyl group (s) (e.g., Nofia OL1000, Nofia OL1001, and Nofia OL3001), tricresyl phosphate (Disflamoll TKP), diphenylcresylphosphate (Disflamoll DPK), tris(isobutylphenyl)phosphate (Disflamoll 50192), 2-ethylhexyl diphenyl phosphate (Disflamoll DPO), triphenyl phosphate (Disflamoll TP), butylated triphenyl phosphate, and combinations thereof.

[0071] In another advantageous aspect of the present invention, phosphorous-containing, flame-retardant compounds which do not contain (meth)acrylate functionality may be present in amounts of about 10% to about 50%, about 15% to about 50%, about 20% to about 50%, about 25% to about 50%, about 30% to about 50%, about 35% to about 50%, about 40% to about 50%, and about 45% to about 50%, percentage by weight of total composition.

[0072] In yet another advantageous aspect of the present invention, phosphorous-containing, flame-retardant compounds which do not contain (meth)acrylate functionality may also be present in amounts of about 10% to about 40%, about 15% to about 40%, about 20% to about 40%, about 25% to about 40%, about 30% to about 40%, about 35% to about 40%, percentage by weight of total composition.

[0073] In yet another advantageous aspect of the present invention, phosphorous-containing, flame-retardant compounds which do not contain (meth)acrylate functionality may also be present in amounts of about 10% to about 30%, about 15% to about 30%, about 20% to about 30%, about 25% to about 30%, percentage by weight of total composition.

[0074] In yet a further advantageous aspect of the present invention, phosphorous-containing, flame-retardant compounds which do not contain (meth)acrylate functionality may also be present in amounts of about 10% to about 20%, about 15% to about 20%, percentage by weight of total composition.

[0075] In a further advantageous aspect of the present invention, the amount of phosphorous present in the phosphorous- containing additive which does not contain (meth)acrylate functionality, may be about 1% to about 30%, about 5% to about 30%, about 10% to about 30%, about 15% to about 30%, about 20% to about 30%, and about 25% to about 30%, all percentages by weight of the phosphorous-containing compound.

[0076] In a further advantageous aspect of the present invention, the amount of phosphorous present in the phosphorous- containing additive which does not contain (meth)acrylate functionality, may be about 1% to about 20%, about 5% to about 20%, about 10% to about 20%, and about 15% to about 20%, all percentages by weight of the phosphorous-containing compound.

[0077] In a further advantageous aspect of the present invention, the amount of phosphorous present in the phosphorous- containing additive which does not contain (meth)acrylate functionality may be about 1% to about 10%, and about 5% to about 10%, all percentages by weight of the phosphorous- containing compound.

[0078] In yet another advantageous aspect of the present invention, the amount of phosphorous present in the phosphorous- containing additive which does not contain (meth)acrylate functionality is desirably about 1% to about 30% percentage by weight of the phosphorous-containing compound.Other Additives

[0079] Optional additives, such as, but not limited to, fluorescence additives, nano-fillers, photosensitizers, coloring agents, accelerators, adhesion promoters, defoamers, stabilizers, antioxidants and pigments, and combinations thereof may be included in the compositions of the present invention.

[0080] In a further advantageous aspect of the present invention, suitable nano-fillers may be present-in amounts of about 1% to about 10%, about 2% to about 10%, about 3% to about 10%, about 4% to about 10%, about 5% to about 10%, about 6% to about 10%, about 7% to about 10%, about 8% to about 10%, and about 9% to about 10%, all percentages weight by total composition.

[0081] In yet another advantageous aspect of the present invention, (meth)acrylate monomers may be present. Suitable (meth)acrylate monomers include, but are not limited to, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate,cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, tolyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ- (methacryloyloxypropyl)trimethoxysilane, (meth)acrylic acid- ethylene oxide adduct, trifluoromethylmethyl (meth)acrylate, 2- trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl(meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2- perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2- perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate. Combinations of these may be used.

[0082] In an advantageous aspect of the present invention, the (meth)acrylate monomer used may be a di(meth)acrylate or a (meth)acrylate-containing di-functional monomer. For example, polyethylene glycol diacrylate, such as SR 259 (a polyethylene glycol (200) diacrylate from Sartomer) may be used. Suitable multifunctional (meth)acrylates include, but are not limited to, polyethylene glycol di(meth)acrylates, and triethyleneglycol di(meth)acrylates, bisphenol-A di(meth)acrylates such as ethoxylated bisphenol-A (meth)acrylate ("EBIPA" OR "EBIPMA") and tetrahydrofuran (meth)acrylates and tetrahydrofuran di(meth)acrylates, citronellyl acrylate and citronellyl methacrylate, hexanediol di(meth)acrylate ("HDDA" or "HDDMA"), trimethylol propane tri(meth)acrylate, tetrahydrodicyclopentadienyl(meth)acrylate, ethoxylatedtrimethylol propane triacrylate ("ETTA"), triethylene glycol diacrylate and triethylene glycol dimethacrylate ("TRIEGMA"), and combinations thereof.

[0083] In a further aspect of the present invention, suitable aromatic (meth)acrylates may be present. Suitable aromatic (meth)acrylates include, but are not limited to, 2-hydroxy-3- phenoxypropyl methacrylate (PHPM), 2-phenoxyethl methacrylate (SR340), ethoxylated 2 bisphenol A dimethacrylate (SR348) and ethoxylated 3 bisphenol A diacrylate (SR349), and combinations thereof.

[0084] The compositions of the present invention may generally have a viscosity of about 100 cPs to about 2,000 cPs, about 200 cPs to about 2,000 cPs, about 300 cPs to about 2,000 cPs, about 400 cPs to about 2,000 cPs, about 500 cPs to about 2,000 cPs, about 600 cPs to about 2,000 cPs, about 700 cPs to about 2,000 cPs, about 800 cPs to about 2,000 cPs, about 900 cPs to about 2,000 cPs, about 1,000 cPs to about 2,000 cPs, about 1,100 cPs to about 2,000 cPs, about 1,200 cPs to about 2,000 cPs, about 1,300 cPs to about 2,000 cPs, about 1,400 cPs to about 2,000 cPs, about 1,500 cPs to about 2,000 cPs, about 1,600 cPs to about 2,000 cPs, about 1,700 cPs to about 2,000 cPs, about 1,800 cPs to about 2,000 cPs, and about 1,900 cPs to about 2,000 cPs.

[0085] In one advantageous aspect of the present invention, the compositions of the present invention generally have a viscosity of about 100 cPs to about 1,000 cPs, about 200 cPs to about 1,000 cPs, about 300 cPs to about 1,000 cPs, about 400 cPs to about 1,000 cPs, about 500 cPs to about 1,000 cPs, about 600 cPs to about 1,000 cPs, about 700 cPs to about 1,000 cPs, about 800 cPs to about 1,000 cPs, and about 900 cPs to about 1,000 cPs.

[0086] In one advantageous aspect of the present invention, the compositions of the present invention are solid at room temperature.

[0087] In one advantageous aspect of the present invention, the compositions of the present invention are flowable at room temperature.

[0088] In one advantageous aspect of the present invention, the compositions of the present invention are a one-part composition.

[0089] In one advantageous aspect of the present invention, the compositions of the present invention are a two-part composition.

[0090] In one advantageous aspect of the present invention, the compositions of the present invention generally have a thermostability residue weight % value as measured by Thermalgravimetric Analysis (TGA) (at 700°C), of about 1% to about 50%, about 2% to about 50%, about 3% to about 50%, about 4% to about 50%, about 5% to about 50%, about 10% to about 50%, about 15% to about 50%, about 20% to about 50%, about 25% to about 50%, about 30% to about 50%, about 35% to about 50%, about 40% to about 50%, and about 45% to about 50%, percentage by weight of total composition.

[0091] In another advantageous aspect of the present invention, the compositions of the present invention generally have a thermostability residue weight % value as measured by Thermalgravimetric Analysis (TGA) (at 700°C), of about 1% to about 40%, about 2% to about 40%, about 3% to about 40%, about 4% to about 40%, about 5% to about 40%, about 10% to about 40%, about 15% to about 40%, about 20% to about 40%, about 25% to about 40%, about 30% to about 40%, and about 35% to about 40%, percentage by weight of total composition.

[0092] In another advantageous aspect of the present invention, the compositions of the present invention generally have a thermostability residue weight % value as measured by Thermalgravimetric Analysis (TGA) (at 700°C), of about 1% to about 30%, about 2% to about 30%, about 3% to about 30%, about 4% to about 30%, about 5% to about 30%, about 10% to about 30%, about 15% to about 30%, about 20% to about 30%, and about 25% to about 30%, percentage by weight of total composition.

[0093] In another advantageous aspect of the present invention, the compositions of the present invention generally have a thermostability residue weight % value as measured by Thermalgravimetric Analysis (TGA) (at 700°C), of about 1% to about 20%, about 2% to about 20%, about 3% to about 20%, about 4% to about 20%, about 5% to about 20%, about 10% to about 20%, and about 15% to about 20%, percentage by weight of total composition.

[0094] In another advantageous aspect of the present invention, the compositions of the present invention generally have a thermostability residue weight % value as measured by Thermalgravimetric Analysis (TGA) (at 700°C), of about 1% to about 10%, about 2% to about 10%, about 3% to about 10%, about 4% to about 10%, about 5% to about 10%, percentage by weight of total composition.

[0095] In another advantageous aspect of the present invention, the compositions of the present invention generally have a thermostability residue weight % value as measured by Thermalgravimetric Analysis (TGA) (at 700°C), of about 1% to about 5%, about 2% to about 5%, about 3% to about 5%, about 4% to about 5%, percentage by weight of total composition.

[0096] In another advantageous aspect of the present invention, the compositions of the present invention generally have a thermostability residue weight % value as measured byThermalgravimetric Analysis (TGA) (at 700°C), of about 1% to about 3%, about 2% to about 3%, percentage by weight of total composition.

[0097] In further advantageous aspect of the present invention, the compositions of the present invention desirably have a thermostability residue weight % value as measured by Thermalgravimetric Analysis (TGA) (at 700°C), of about 1% to about 50% percentage by weight of total composition.

[0098] In one advantageous aspect of the present invention, the compositions of the present invention generally have a self- flame-extinguishing time, as measured by burning the composition for 30 seconds ("s") on a 3mm disk, of about 0 s to about 15 s, about 1 s to about 15 s, about 2 s to about 15 s, about 3 s to about 15 s, about 4 s to about 15 s, about 5 s to about 15 s, about 6 s to about 15 s, about 7 s to about 15 s, about 8 s to about 15 s, about 9 s to about 15 s, about 10 s to about 15 s, about 11 s to about 15 s, about 12 s to about 15 s, about 13 s to about 15 s, and about 14 s to about 15 s.

[0099] In one advantageous aspect of the present invention, the compositions of the present invention generally have a self- flame-extinguishing time, as measured by burning the composition for 30 seconds ("s") on a 3mm disk, of about 0 s to about 5 s, about 0 to about 8 s, about 0 to about 10 s, about 1 to about 5 s, about 2 to about 8 s, and about 5 to about 10 s.

[0100] In one advantageous aspect of the present invention, an article of manufacture may be made from the compositions of the present invention. The article of manufacture may be selected any number of articles where flame retardancy is useful. For example, the compositions may be employed as motor vehicle interiors and motor vehicle products, aviation interiors and aviation products, battery housings, train interiors andproducts, structure interiors including seats and compartments, marine vessels and products, to name a few.

[0101] The applications of the compositions of this invention include, but are not limited to use as adhesives, sealants, coatings, interior matrix resins, and combinations thereof.Clauses

[0102] [Clause 1] A flame-retardant resin composition including: a) one or more nitrogen-containing (meth)acrylate reactive component(s), b) one or more phosphorous-containing (meth)acrylate reactive component(s), and c) at least one cure system, wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing (meth)acrylate reactive component(s) is from about 1 to 1 to about 10 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of total composition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.

[0103] [Clause 2] The composition of clause 1, wherein the nitrogen-containing (meth)acrylate reactive component(s) is selected from the group consisting of tris(2- hydroxyethyl)isocyanurate triacrylate, 4-acryloylmorpholine, N,N-dimethylacrylamide, N-vinylpyrrolidone, 1-Vinylimidazole triallyl-isocyanurate, and combinations thereof.

[0104] [Clause 3] The composition of any one of clauses 1-2, wherein phosphorous-containing (meth)acrylate reactive component(s) is selected from the group consisting of bis HEMA phosphate, phosphorus-containing di-functional acrylatedoligomer, 2-hydroxyethyl-methacrylate-phosphate, 2-hydroxyethyl methacrylate phosphate, and combinations thereof.

[0105] [Clause 4] The composition of any one of clauses 1-3, wherein the nitrogen-containing (meth)acrylate reactive component(s) is present in an amount of about 20% to about 80% percent by weight of the total composition.

[0106] [Clause 5] The composition of any one of clauses 1-4, wherein the phosphorous-containing (meth)acrylate reactive component(s) is present in an amount of about 10% to about 50% percent by weight of the total composition.

[0107] [Clause 6] The composition of any one of clauses 1-5, wherein the amount of phosphorous present in the phosphorous- containing (meth)acrylate reactive component(s) is about 5% to about 20% percent by weight of the phosphorous-containing (meth)acrylate.

[0108] [Clause 7] The composition of any one of clauses 1-6, wherein the cure system is selected from the group consisting of a heat curing system, a photo-curing system, a chemical curing system and combinations thereof.

[0109] [Clause 8] The composition of any one of clauses 1-7, wherein the ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing (meth)acrylate reactive component(s) is from about 1 to 1 to about 3 to 1.

[0110] [Clause 9] The composition of any one of clauses 1-8, wherein the composition is free of fillers which are greater than nano-sized particles.

[0111] [Clause 10] The composition of any one of clauses 1-9, wherein the composition contains nano-sized fillers.

[0112] [Clause 11] The composition of any one of clauses 1- 10, wherein the composition further includes a phosphorous- containing non-(meth)acrylate, flame-retardant additive selected from the group consisting of phosphorous-based oligomer havingphenolic hydroxyl, tricresyl phosphate, diphenylcresylphosphate, tris(isobutylphenyl)phosphate, 2-ethylhexyl diphenyl phosphate, triphenyl phosphate, butylated triphenyl phosphate, and combinations thereof.

[0113] [Clause 12] The composition of any one of clauses 1-11, wherein the phosphorous-containing non-(meth)acrylate, flame-retardant additive is present in an amount of about 1% to about 30% percent by weight of the total composition.

[0114] [Clause 13] The composition of any one of clauses 1-12, wherein the composition further includes a nitrogen- containing non-(meth)acrylate, flame-retardant additive selected from the group consisting of melamine, melamine derivatives such as melamine cyanurate, melamine polyphosphate, melamine borate, melamine ammonium, Guanidine and its salts, N-alkoxy hindered amines,azoalkanes, phosphazenes, phospham, and combinations thereof.

[0115] [Clause 14] The composition of any one of clauses 1-13, wherein the nitrogen-containing non-(meth)acrylate, flame- retardant additive is present in an amount of about 1% to about 30% percent by weight of the total composition.

[0116] [Clause 15] The composition of any one of clauses 1-14, wherein the nitrogen-containing (meth)acrylate reactive component(s) further comprises a nano-silica-filler.

[0117] [Clause 16] The composition of any one of clauses 1-15, wherein the nano-silica-filler comprises hexanedioldiacrylate nanosilica particles, trimethylolpropane triacrylate with 50% nanosilica, hydroxyethyl methacrylate with 50% nanosilica, and combinations thereof.

[0118] [Clause 17] The composition of any one of clauses 1-16, wherein the nano-silica-filler is present in an amount of about 1% to about 30% percent by weight of the total composition.

[0119] [Clause 18] The composition of any one of clauses 1-17, wherein the cure system further comprises a photoinitiator present in an amount of about 0.5% to about 5% percent by weight of the total composition.

[0120] [Clause 19] The composition of any one of clauses 1-18, wherein the cure system comprises a metal catalyst and a peroxide present in a combined amount of about 0.5% to about 5% percent by weight of the total composition.

[0121] [Clause 20] The composition of any one of clauses 1-19, wherein the cure system comprises a thermal initiator present in an amount of about 0.5% to about 5% percent by weight of the total composition.

[0122] [Clause 21] The composition of any one of clauses 1-20, wherein the composition is flowable at room temperature.

[0123] [Clause 22] The composition of any one of clauses 1-21, wherein the viscosity is about 2,000 cPs or less at room temperature.

[0124] [Clause 23] The composition of any one of clauses 1-22, wherein the composition is solid at room temperature.

[0125] [Clause 24] The composition of any one of clauses 1-23, wherein the composition is a one-part composition.

[0126] [Clause 25] The composition of any one of clauses 1-24, wherein the composition is a two-part composition.

[0127] [Clause 26] A flame-retardant reaction product including the reaction of: a) one or more nitrogen-containing (meth)acrylate reactive component(s), b) one or more phosphorous-containing (meth)acrylate reactive component(s), and c) at least one cure system,wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing (meth)acrylate reactive component(s) is from about 1 to 1 to about 10 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of total composition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.

[0128] [Clause 27] An article of manufacture made from the composition of any one of clauses 1-26.

[0129] [Clause 28] The article of manufacture of any one of clauses 1-27, selected from the group consisting of motor vehicle interiors and products, aviation interiors and products, battery housings, train interiors and products, structure interiors including seats and compartments, marine vessels and products.

[0130] [Clause 29] A flame-retardant composition including: a) a nitrogen-containing (meth)acrylate reactive component selected from the group consisting of tris(2-hydroxyethyl)isocyanurate triacrylate, 4- acryloylmorpholine, and combinations thereof, b) a phosphorous-containing (meth)acrylate reactive component selected from the group consisting of bis hydroxyethyl (meth)acrylate phosphate, 2-hydroxyethyl (meth)acrylate phosphate, and combinations thereof, c) at least one cure system, and ' wherein a ratio of nitrogen-containing (meth)acrylate reactive component to phosphorous-containing (meth)acrylate reactive component is from about 1 to 1 to about 3 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 20% to about 30% by weight oftotal composition, and / or a flame extinguishing time of about 0 seconds to about 10 seconds when burned for 30 seconds.

[0131] [Clause 30] A flame-retardant resin composition including: a) one or more nitrogen-containing (meth)acrylate reactive component(s), b) one or more phosphorous-containing non-(meth)acrylate additive component(s), and c) at least one cure system, wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing non- (meth)acrylate additive component(s) is from about 1 to 1 to about 10 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of total composition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.

[0132] [Clause 31] The composition of any one of clauses 1-30, wherein the nitrogen-containing (meth)acrylate reactive component(s) is present in an amount of about 20% to about 80% percent by weight of the total composition.

[0133] [Clause 32] The composition of any one of clauses 1-31, wherein the phosphorous-containing non-(meth)acrylate additive component (s) is present in an amount of about 10% to about 50% percent by weight of the total composition.

[0134] [Clause 33] The composition of any one of clauses 1-32, wherein the phosphorous-containing non-(meth)acrylate additive component(s) is selected from the group consisting of phosphorous-based oligomer having phenolic hydroxyl, tricresyl phosphate, diphenylcresylphosphate, tris(isobutylphenyl)phosphate, 2-ethylhexyl diphenyl phosphate,triphenyl phosphate, butylated triphenyl phosphate, and combinations thereof.

[0135] [Clause 34] A method of making a flame-retardant composition including the steps of: a) combining one or more nitrogen-containing (meth)acrylate reactive component(s), with b) one or more phosphorous-containing (meth)acrylate reactive component(s), c) at least one cure system, and wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing (meth)acrylate reactive component(s) is from about 1 to 1 to about 10 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of total composition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.EXAMPLESTesting MaterialsGel Time:

[0136] Pour 6g of mixed the curable composition into a 4.5 cm diameter aluminum pan. Use wooden stick to check the mixed material every 5 minutes until it does not adhere to the wooden stick. Record this time as Gel time, as referred to as working time.Self-extinguish time fromVertical Burning Flame Retardancy Test:

[0137] The Sample Flame Retardancy test is modified from UL94-V which is used to determine the flammability of a specified material and the burn time associated with it.

[0138] Sample preparation: Put 5 grams of the curable composition into 4.5 cm diameter aluminum pan and then cure the material by photo-cure, chemical (redox) cure and / or heat cure forming a puck with thickness around 3mm. For photo-cure (meth)acrylate compositions, cure the material for 10s usingHenkel EQ CL20 LED Flood 405 nm with a light intensity of 1.2w / cm2. For chemical (redox) cure compositions, cure the composition at RT until it is completely hardened. For heat cure compositions, cure the composition in an 80°C oven for 2hrs or until it is completely hardened. Clamp the sample into a fixture assembly with an approximately % inch distance from a Bunsen burner. The height for burner flame is approximately 1.5 inches. Burn the middle of the sample for 30 seconds, whereupon immediately after the removal of the flame, measure the time when the flame completely disappeared as the Self-extinguish time.Residue at 700°C from Thermogravimetric Analysis (TGA):

[0139] The curable composition was placed between two plastic sheets with a 1 mm thick spacer and then covered with glass slides. For photo-cure (meth)acrylate compositions, cure the material for 10s using Henkel EQ CL20 LED Flood 405 nm with a light intensity of 1.2w / cm2. For chemical (redox) cure compositions, cure the composition at RT until it is completely hardened. For heat cure compositions, cure the composition in an 80°C oven for 2hrs or until it is completely hardened. A small sample of cured composition is cut from the cured material placed in a TGA instrument TA Discovery TGA. The temperature is increased from room temperature (approximately 25°C) to 700°C with the air flow of 25ml / min and heating rate of 20 °C / minute. The weight% of the Residue at 700°C is recorded.Viscosity:

[0140] Viscosity was measured with a conical plate having a diameter of 25 mm and a 2-degree cone angle using a cone and plate rheometer (Anton Paar). Viscosity was measured at a rateof 10 reciprocal seconds at 25 °C with a shear ramp from 0.1 reciprocal seconds to 50 reciprocal seconds.Example 1

[0141] Inventive Composition 1.9 and Comparative examples 1.1-1.8 were prepared using the formulations set forth in Table 1. A nitrogen-containing (meth)acrylate reactive component, tris(2-Hydroxyethyl) isocyanurate triacrylate (SR368, melting point of 52°C to 54°C) was melted in a 80 °C oven and then mixed using a high speed mixer with other lower-viscosity(meth)acrylate liquid resins and a photoinitiator (Omnirad TPO- L) in a weight ratio of 70 / 28 / 2 (according to the formulations in Table 1. Visiomer HEMA 98 and Visiomer HPMA 98 are non-N or P containing (meth)acrylate resins with hydroxyl groups. SR340, PHPM, SR348, and SR349 are non-N or P containing aromatic (meth)acrylate resins. NNDMA and ACMO are nitrogen-containing (meth)acrylate reactive component. Visiomer HEMA P100 is a phosphorous-containing (meth)acrylate reactive component.

[0142] Table 2 is the summary of the viscosity, Residue wt% at 700°C from TGA and Self-extinguish time from Vertical burning Flame Retardancy test.* Not measured due to resin solidification

[0143] Table 2 shows that Inventive Example 1.9 with a nitrogen-containing (meth)acrylate reactive component being tris(2-Hydroxyethyl) isocyanurate triacrylate and a P- containing (meth)acrylate reactive component being Visiomer HEMA-P100 shows the highest residue wt% 30.5% at 700 °C and the lowest Self-extinguish time (0s). All comparative examples have Residue wt% of less than 1% and a Self-extinguish time >60s, indicating low flammability retardancy.

[0144] Inventive Example 1.9 solidifies at room temperature, which may not be desirable for all applications. Therefore, it may be desirable to mix the composition of Inventive Example 1.9(or a similar inventive composition) with low viscosity monomers or additives to achieve flowability at room temperature.Example 2

[0145] In this example, the nitrogen-containing(meth)acrylate reactive component tris(2-Hydroxyethyl) isocyanurate triacrylate (SR368) was mixed with a phosphorous- containing non-(meth)acrylate flame retardant additives (i.e., phosphorous-containing retardants having no (meth)acrylate functionality) such as Disflamoll, as well as Nofia Phosphonate Oligomers. The compositions and mixing ratios are shown in Table 3. Inventive examples 2.1 to 2.7 contain Disflamoll TKP, DPK, DPO and TP with or without ACMO, a nitrogen-containing low viscosity monomer. Inventive examples 2.8 to 2.11 contain Disflamoll 51092, Nofia 1001 and Nofia 3001 with or without ACMO.

[0146] Table 4'is the summary of the viscosity, Residue wt% at 700°C from TGA and Self-Extinguish Time from the Vertical Burning Flame Retardancy test.* Not measured due to resin solidification

[0147] Table 4 shows that the Inventive Examples 2.8-2.11 with a nitrogen-containing (meth)acrylate reactive component being tris(2-Hydroxyethyl) isocyanurate triacrylate, aphosphorous-containing (meth)acrylate reactive component being Visiomer HEMA-P100, phosphorous-containing non-(meth)acrylate additives Disflamoll 51092, Nofia 1001 and Nofia 3001 with or without ACMO, have >5% of residue wt% at 700 °C and a Self- Extinguish time <3s. The Self-Extinguish time for Inventive Examples 2.1-2.3 and 2.5-2.6 are less 5s, Inventive Example 2.7 is 7s, and Inventive Example 2.7 is greater than 60s. The higher flammability retardancy performance of Disflamoll 51092 comparing to other Disflamoll additives used in the examples may be due to it containing non-substituted aromatic structures.Example 3

[0148] In this example, the nitrogen-containing(meth)acrylate reactive component tris(2-Hydroxyethyl) isocyanurate triacrylate (SR368), ACMO, and NNDMA were mixed with a phosphorous-containing (meth)acrylate flame retardant reactive component Harcryl 1228 (same as Visiomer HEMA P-100), Non-(meth)acrylate containing flame retardant additive Disflamoll 51092, as well as Nofia Phosphonate Oligomers Nofia 1001 and 3001 in different ratio from those examples in Examples 1 and 2. The inventive example compositions and mixing ratios are shown in Table 5.

[0149] Table 6 is the summary of the viscosity, Residue wt% at 700°C from TGA and Self-Extinguish time from Vertical Burning Flame Retardancy test.

[0150] All of these inventive examples showed a wt% of >5% residue at 700 °C and a Self-Extinguish time of <5s (Table 6).Example 4

[0151] In this example, one (meth)acrylate composition (Inventive Example 4.1), substantially similar to the resin base of photo-cured Inventive Example 3.2, was studied using a chemical curing method (at room temperature). The composition is shown in Table 7, below. The oxidant CHP, reducing agent PDHP,as well as catalyst 8% Cu NAP, were mixed into the composition for chemical cure.

[0152] Table 8 is the summary of the viscosity, Residue wt% at 700°C from TGA, Self-extinguish time from Vertical burning Flame Retardancy test and gel set times.

[0153] The Inventive Example 4.1, in Table 8 above, showed>5% of residue at 700 °C and a Self-Extinguish time of <5s.These results show that the inventive flame-retardant(meth)acrylate-based compositions were able to be cured usingchemical curing at room temperature with defined gel time and set time.Example 5

[0154] In this example, various (meth)acrylate compositions (Inventive Examples 5.1-5.4), resembling the resin base of photo-cured Inventive Examples 3.3-3.6, were studied using heat cure (at 80°C). The compositions are shown in Table 9, below. Benzoyl peroxide (Luperox A75), as a thermal initiator, was dispersed in Disflamoll 51092 in a weight ratio of 1:9 and then mixed with the (meth)acrylate resins.

[0155] Table 10 is the summary of the viscosity, Residue wt% at 700°C from TGA, Self-Extinguish time from Vertical Burning Flame Retardancy test and gel set times.

[0156] The Inventive heat cured Examples in Table 10 above, also exhibited >5% of residue at 700 °C and Self-Extinguish time <5s. These results show that the inventive flame-retardant (meth)acrylate-based compositions were able to be formulated using heat cure systems and cured by heat (at 80°C), with adjustable set time.Example 6

[0157] In this example, photo-cured (meth)acrylate resins with various conventional (non-nano sized) flame-retardant fillers were studied (Comparative Examples 6.1-6.3). Conventional fillers, including AEROSIL R202 (Silica), Exolit AP 462 (ammonium polyphosphate), or Mxl04 (alumina trihydrate) were mixed with the (meth)acrylate resins and photoinitiators as shown in Table 11, below. Due to viscosity limitations, only about 3 wt.% of R202 was added to the resin, while the other two fillers can be included up to about 30 wt.% and still have acceptable viscosities. The appearance of the as-prepared resins with various fillers were recorded, and viscosity was measured. The mixed resins were photo-cured using LED 405 nm lamp with a light intensity of 1.2 W / cm2for 10s. The burning test results of the cured resins, along with other properties are summarized in Table 12, below.

[0158] (Meth)acrylate resin compositions with conventional- sized fillers (as opposed to nano-sized filler) can bring about different issues. In Comparative Example 6.1, addition of regular silica makes the resin thixotropic with a high viscosity. However, the resin still failed the burning test. In Comparative Example 6.2, ammonium polyphosphate provided great flame retardancy to the (meth)acrylate resin composition, but fast phase separation occurred for the mixture, which is not acceptable for processing. Similarly, introduction of alumina trihydrate lead to phase separation, contributing to the resin failing the burning test.

Claims

Claims:

1. A flame-retardant resin composition comprising: a) one or more nitrogen-containing (meth)acrylate reactive component(s), b) one or more phosphorous-containing (meth)acrylate reactive component(s), and c) at least one cure system, wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing (meth)acrylate reactive component(s) is from about 1 to 1 to about 10 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of total composition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.

2. The composition of claim 1, wherein the nitrogen- containing (meth)acrylate reactive component(s) is selected from the group consisting of tris(2-hydroxyethyl)isocyanurate triacrylate, 4-acryloylmorpholine, N,N-dimethylacrylamide, N- vinylpyrrolidone, 1-vinylimidazole triallyl-isocyanurate, and combinations thereof.

3. The composition of claim 1, wherein phosphorous- containing (meth)acrylate reactive component(s) is selected from the group consisting of bis HEMA phosphate, phosphorus- containing di-functional acrylated oligomer, 2-hydroxyethyl- methacrylate-phosphate, 2-hydroxyethyl methacrylate phosphate, and combinations thereof.

4. The composition of claim 1, wherein the nitrogen- containing (meth)acrylate reactive component(s) is present in an amount of about 20% to about 80% percent by weight of the total composition.

5. The composition of claim 1, wherein the phosphorous- containing (meth)acrylate reactive component(s) is present in an amount of about 10% to about 50% percent by weight of the total composition.

6. The composition of claim 1, wherein the amount of phosphorous present in the phosphorous-containing (meth)acrylate reactive component(s) is about 5% to about 20% percent by weight of the phosphorous-containing (meth)acrylate.

7. The composition of claim 1, wherein the cure system is selected from the group consisting of a heat curing system, a photo-curing system, a chemical curing system and combinations thereof.

8. The composition of claim 1, wherein the ratio of nitrogen-containing (meth)acrylate reactive component (s) to phosphorous-containing (meth)acrylate reactive component(s) is from about 1 to 1 to about 3 to 1.

9. The composition of claim 1, wherein the composition is free of fillers which are greater than nano-sized particles.

10. The composition of claim 1, wherein the composition contains nano-sized fillers.

11. The composition of claim 1, wherein the composition further comprises a phosphorous-containing non-(meth)acrylate, flame-retardant additive selected from the group consisting of phosphorous-based oligomer having phenolic hydroxyl, tricresyl phosphate, diphenylcresylphosphate, tris(isobutylphenyl)phosphate, 2-ethylhexyl diphenyl phosphate, triphenyl phosphate, butylated triphenyl phosphate, and combinations thereof.

12. The composition of claim 11, wherein the phosphorous- containing non-(meth)acrylate, flame-retardant additive is present in an amount of about 1% to about 30% percent by weight of the total composition.

13. The composition of claim 1, wherein the composition further comprises a nitrogen-containing non-(meth)acrylate, flame-retardant additive selected from the group consisting of melamine, melamine derivatives such as melamine cyanurate, melamine polyphosphate, melamine borate, melamine ammonium, Guanidine and its salts, N-alkoxy hindered amines,azoalkanes, phosphazenes, phospham, and combinations thereof.

14. The composition of claim 13, wherein the nitrogen- containing non-(meth)acrylate, flame-retardant additive is present in an amount of about 1% to about 30% percent by weight of the total composition.

15. The composition of claim 1, wherein the nitrogen- containing (meth)acrylate reactive component(s) further comprises a nano-silica-filler.

16. The composition of claim 15, wherein the nano-silica- filler comprises hexanedioldiacrylate nanosilica particles, trimethylolpropane triacrylate with 50% nanosilica, hydroxyethyl methacrylate with 50% nanosilica, and combinations thereof.

17. The composition of claim 15, wherein the nano-silica- filler is present in an amount of about 1% to about 30% percent by weight of the total composition.

18. The composition of claim 1, wherein the cure system further comprises a photoinitiator present in an amount of about 0.5% to about 5% percent by weight of the total composition.

19. The composition of claim 1, wherein the cure system comprises a metal catalyst and a peroxide present in a combined amount of about 0.5% to about 5% percent by weight of the total composition.

20. The composition of claim 1, wherein the cure system comprises a thermal initiator present in an amount of about 0.5% to about 5% percent by weight of the total composition.

21. The composition of claim 1, wherein the composition is flowable at room temperature.

22. The composition of claim 1, wherein the viscosity is about 2,000 cPs or less at room temperature.

23. The composition of claim 1, wherein the composition is solid at room temperature.

24. The composition of claim 1, wherein the composition is a one-part composition.

25. The composition of claim 1, wherein the composition is a two-part composition.

26. A flame-retardant reaction product comprising the reaction of: a) one or more nitrogen-containing (meth)acrylate reactive component(s), b) one or more phosphorous-containing (meth)acrylate reactive component(s), and c) at least one cure system, wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing (meth)acrylate reactive component(s) is from about 1 to 1 to about 10 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of total composition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.

27. An article of manufacture made from the composition of claim 1.

28. The article of manufacture of claim 27, selected from the group consisting of motor vehicle interiors and products, aviation interiors and products, battery housings, train interiors and products, structure interiors including seats and compartments, marine vessels and products.

29. A flame-retardant composition comprising: a) a nitrogen-containing (meth)acrylate reactive component selected from the group consisting of tris(2-hydroxyethyl)isocyanurate triacrylate, 4- acryloylmorpholine, and combinations thereof, b) a phosphorous-containing (meth)acrylate reactive component selected from the group consisting of bis hydroxyethyl (meth)acrylate phosphate, 2-hydroxyethyl (meth)acrylate phosphate, and combinations thereof, c) at least one cure system, and wherein a ratio of nitrogen-containing (meth)acrylate reactive component to phosphorous-containing (meth)acrylate reactive component is from about 1 to 1 to about 3 to 1, and wherein subsequent to cure, the ratio imparts flame- retardant properties to the composition as measured by a TGA residue amount of at least about 20% to about 30% by weight of total composition, and / or a flame extinguishing time of about 0 seconds to about 10 seconds when burned for 30 seconds.

30. A flame-retardant resin composition comprising: a) one or more nitrogen-containing (meth)acrylate reactive component(s), b) one or more phosphorous-containing non-(meth)acrylate additive component(s), and c) at least one cure system, wherein a ratio of nitrogen-containing (meth)acrylate reactive component(s) to phosphorous-containing non- (meth)acrylate additive component(s) is from about 1 to 1 to about 10 to 1, and wherein subsequent to cure, the ratio imparts flame-retardant properties to the composition as measured by a TGA residue amount of at least about 1% to about 50% by weight of totalcomposition, and / or a flame extinguishing time of about 15 seconds or less when burned for 30 seconds.

31. The composition of claim 30, wherein the nitrogen- containing (meth)acrylate reactive component(s) is present in an amount of about 20% to about 80% percent by weight of the total composition.

32. The composition of claim 30, wherein the phosphorous- containing non-(meth)acrylate additive component(s) is present in an amount of about 10% to about 50% percent by weight of the total composition.

33. The composition of claim 30, wherein the phosphorous- containing non-(meth)acrylate additive component(s) is selected from the group consisting of phosphorous-based oligomer having phenolic hydroxyl, tricresyl phosphate, diphenylcresylphosphate, tris(isobutylphenyl)phosphate, 2-ethylhexyl diphenyl phosphate, triphenyl phosphate, butylated triphenyl phosphate, and combinations thereof.

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