In a preferred embodiment, the photoinitiator includes one or more of bisacyl phosphine oxide; Diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide; ethyl(2,4,6-trimethylbenzoyl)-phenyl phosphinate (TPO-L); and bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (Irgacure 819/BAPO).

In one embodiment, the radical inhibitors may include one or more of N-nitrosophenylhydroxylamine; hydroquinone and derivatives; monomethyl ether hydroquinone; benzoquinone; methoxy hydroquinone; tert butyl catechol; phenothiazine; or pyrogallol. In one aspect, the inhibitors prevent the acrylate monomer photopolymerization from occurring before being activated by light. In a preferred embodiment, the radical inhibitors includes one or more of N-nitrosophenylhydroxylamine; pyrogallol; 1,4-benzenediol, 1,4-Dihydroxybenzene (HQ); 4-hydroxyanisole (MEHQ); N-nitorosophenylhydroxylamine aluminum salt (Q1301); and combinations thereof.

In one embodiment, the surface additives to reduce surface tension can include one or more silicone-containing surface additive that are solvent-free, solvent-borne and aqueous coating systems, printing inks and adhesive systems as well as ambient-curing plastic systems that have strong reduction of surface tension. Non-limiting examples of suitable surface additives include one or more silicone-containing surface additive or other non-silicone containing surface additives, e.g., polyacrylate-based additives. In one embodiment, the additives are solvent-free, solvent-borne and aqueous coating systems, printing inks and adhesive systems as well as ambient-curing plastic systems that have strong reduction of surface tension. In one embodiment, the surface additive is a crosslinking, silicone-containing surface additive. In one embodiment, the additive is non-toxic, e.g., it can be used for food contact applications and can include one or more surface additive from BYK, e.g., BYK-333; BYK-UV-3576; BYK-361 N; BYK-1794; BYK-1790; BYK-UV-3575; BYK-UV-3500, and BKUV-3575 and combinations of the same. Other In a non-preferred embodiment, the surface additive to reduce surface tension is a polyacrylate-based surface additive.

In one embodiment, one or more performance additives can include one or more of a UV protectant additive, abrasion resistance additive, adhesion promoter additive, algicide additive, antifoaming additives, antimarring additive, antirust additive, antiscratch resistance additive, antiskid additive, bactericides additive, corrosion inhibitor additive, flame retardant additive, flash rust inhibitor additive, flattening additive, fungicide additive, flow or leveling additive, fungicide additive, anti-weathering additive, matting flatting additive, surfactant additive, suspension additive, and thickening additive, as known in the art.

In one embodiment, the UV protectant additive is configured to prevent or minimize damage from the sun, e.g., Omnistab 1130 from IGM (CAS NO. 25322-68-3+104810-48-2+104810-47-1) and others as known in the art.

In one embodiment, the fire retardant additives may include one or more of phosphate methacrylate, ethylene glycol methacrylate phosphate, phosphoric acid 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate phosphate, 4-Hydroxybutyl Acrylate Phosphate, phosphate esters of hydroxyalkyl acrylates and hydroxyalkyl methacrylates, Miwon's Miramer SC1400 (proprietary phosphate methacrylate); Esstech Item #X-744-0000, HEMA Phosphate, Miwon's Miramer SC1400A (proprietary phosphate acrylate). In a preferred embodiment, these include Miramer SC1400 and Miramer SC1400A.

In one embodiment, the defoaming additives may include modified polydimethylsiloxanes, for example Dehydran 1293, 2293 as well as EFKA 2550, 2580, Foamstar A38, and MF324 offered by BASF, Drewplus S4374 by Ashland, Airex 901W, Foamex 805, and 822 by Theo Goldschmidt, Borchi Gol LA200 and Bochers AF0670 by OMG Borchers. Of course, other defoaming agents as known in the art may be utilized. The defoaming agents are capable of suppressing or making the foaming bubbles burst. In a preferred embodiment, defoaming agents are matched to the respective aqueous system and application.

In one embodiment, the solvents may include one or more of alcohol, methanol, ethanol, isopropanol (IPA), toluene tetrahydrofuran (THF), and dimethyl sulfoxide (DMSO). Acetone is not a suitable solvent and is thought to be incompatible with compositions described herein. Therefore, the composition is acetone free, without acetone or does not include an acetone component.

In one embodiment, the glass/silica fillers may include one or more of a silica particle; Kevlar veil; PET mesh; fiber mesh; metal mesh; Multi-Walled Carbon NanoTube (MWCNTs); carbon nanotubes (CNTs); organoclay; clays; alumina; titania; zirconia; carbon, bioglass (or bioactive glass); hydroxyapatite (HA) particle/mesh; quartz, barium glass; barium salt; titanium dioxide; and combinations thereof. In a preferred embodiment the glass/silica include fumed silica particle.

In one embodiment, the pigments may include one or more conventional pigments, such as titanium dioxide, iron oxides, zinc phosphate, zinc sulfide, zinc oxide, barium sulfate, magnesium silicate and corrosion inhibiting pigments, e.g., strontium chromate, zinc phosphate and barium metaborate, can be included. Optionally and/or alternately, the pigments may include a matting agent to adjust the sheen or gloss, e.g., matte finish, semi-gloss finish, gloss finish, satin finish, eggshell finish, and the like.

There are several methods of using the energy curable compositions, e.g., methods as described with reference to U.S. patent application Ser. No. 15/593,985, which is hereby incorporated by reference as if fully set forth herein. Each of the methods disclosed in U.S. patent application Ser. No. 15/593,985 are incorporated by reference as if fully set forth herein.

In one embodiment, various methods of using the energy curable materials described herein include using the energy curable material as decorative and/or protective coating on interior and exterior surfaces of: aircraft, automotive, recreational vehicles, watercraft, furniture and cabinetry, hardwood flooring, such as solid and engineered laminates, fishing tackle such as coating lures and baits, fiber reinforced fishing rods, fiber reinforced water sports equipment such as but not limited to: surfboards, wakeboards, bodyboards, water skis, skim boards, paddle boats, etc., fiber reinforced bath ware, spas, and hot tubs, fiber reinforced body panels for automotive, recreational vehicles, and watercraft.

In one embodiment, the energy curable material is used a laminating resin as described with reference to U.S. patent application Ser. No. 15/593,985, which is hereby incorporated by reference for that purpose. In one embodiment, the energy curable resin is used a filling agent or coating for the manufacture and repair of: fishing tackle such as coating lures, baits, fiber reinforced fishing rods, fiber reinforced water sports equipment such as but not limited to: surfboards, wakeboards, bodyboards, water skis, skim boards, paddle boats, etc., fiber reinforced bath ware, spas, pools, hot tubs, fiber reinforced body panels for automotive, recreational vehicles, watercraft, vehicle paneling such as those for recreational vehicle compartment walls, acoustic panels, aircraft interior cabinetry, fiber reinforced construction applications such as retention barriers for window wells, replications of construction facades such as decorative rock for building fronts, millwork, or ornamentations, structural chips, cracks, breaks, punctures or voids in composite matrix products, fiberglass, acrylic, glass, ceramic, porcelain, tile, natural, manmade stone, concrete, any solid material to add substance where material is lacking creating a new surface to provide for continuity, restoration, repair, etc. that is sandable, paintable, and can be tooled and conformed.

In one embodiment, the energy curable resin is used a general bonding material for two or more materials such as securing the windings over the guide to the rod on a fishing rod, securing windings on a fishing fly, securing electrical windings on motors, or any other process where the materials to be bonded are both covered and irradiated. The energy curable composition can also be used as an anti-tampering coating useful for indicating a break in safety protocols requiring the physical security of an object within a storage container or device.

In one embodiment, the energy curable resin herein has more than purpose, e.g., it can be used a topcoat, e.g., clear coating, a fire retardant coating, a water protective coating, a weather protective coating, an anti-corrosion protective coating, a sealant coating, e.g., cement sealer, wood sealer, a stain coating, an improved holdout coating combinations of the same and the like. In one embodiment, the cured coating is non-porous.

In one embodiment, the energy curable material can be added to a mold, e.g., transparent or non-transparent, to form a three-dimensional structure. The material can be cured as described herein and optionally heated and cooled. The energy curable material can be cured to a depth in a range from less than 1 mm to about 40 mm or less, in a preferred embodiment the cure depth is less than 1 mm. One embodiment of the invention is directed towards filing cracks in concrete or similar material and curing the material and curing the material in-situ.

Holdout means the ability of a coating to remain at or near the surface of a substrate, as opposed to penetrating that substrate. Better holdout results in the appearance of a smoother, more uniform coated surface with increased gloss and depth as compared to a coated substrate with less holdout. This is true even though the same dry film thickness of coating may have been applied to both substrates. For instance, in a porous substrate, when a coating is applied, the coating may absorb or permeate into the substrate. One embodiment of the invention is directed towards a method that reduces the amount of the coating absorbed into the substrate, allowing more of the coating to remain at or near the surface of the substrate. By increasing holdout in this manner, the resulting substrate has a smoother overall surface, and the substrate requires a fewer number of coatings. By reducing the number of required coatings, the invention also provides the advantages of reducing labor and material costs, while maintaining a coating with desirable properties. Moreover, increased or improved holdout means decreased fiber raising and increased moisture resistance. It is believed, the substrate will require a fewer number of coatings to achieve a desired finish. It is also believed the invention will lead to reduced processing time and reduced labor and material costs. Moreover, it is believed the invention provides a way to size a three-dimensional substrate. It is further believed the substrate produced by the process of the invention will typically display an increased stiffness, strength, smoothness and/or weight. It is further believed the invention can produce a sized or pretreated board that is compatible with a variety of overcoats. In one embodiment, the invention is directed towards man-made fiber boards, such as low density, medium density and high density fiber boards, for example.

Tack free is the ability of a coating to not be sticky on the surface as opposed to coating that it is sticky on a surface. Tack free time is equal to or less than the curing time and means the applied coating is no longer sticky to the touch.

One embodiment is directed towards a method of resurfacing or coating a material or substrate. The material or substrate may be a preexisting material including one or more of cement, wood, plater, plastic, fiberglass, thermoplastics, and combinations of the same. For example, the material may be worn or used swimming pool surface including at least one or more of chips, cracks, mold, algae, and combinations of the same. The resurfacing method includes cleaning and drying the cement surface. The method includes applying the energy curable material to the material or substrate by any conventional technique, e.g., spray, paint brush, roller, combinations of the same or the like, to a predetermined thickness. In a preferred embodiment, the thickness of the wet coating is in a range from about 2 mils to about 5 mils. Next, an energy source as described herein, e.g., having wavelength in a range from about 360nm to about 420 nm at a surface power output less than about 400 mW/cm²was applied to cure the material for about two minutes or less. Of course, other curing surface power densities higher or lower, curing times higher or lower and/or performance additives may also be utilized as described herein. These steps are repeated until the desired thickness is achieved. Optionally, and/or alternatively, the energy source may be dynamically adjusted as described herein, e.g., be pulsed, ramped non-linearly, ramped linearly or combination as described herein. Moreover, an additional heating and cooling step may be done to a cured coating or article in a furnace and cooler. The heating may be done a temperature of about 100 degrees to about 180 degrees Fahrenheit or higher and the cooler is done below room temperature to freezing or lower each for a predetermined amount of time, e.g., 30 mins to 2 hours greater.

One embodiment of the invention is directed towards filling cracks in a substrate, e.g., a cement substrate. The cracks can be prefilled with a packing material, e.g., fiberglass rope that is coated or uncoated to prefill the crack. The packing material may include any composite material as known in the art. If the packing material coated and/or saturated with the energy curable material it can cure to a solid material as with the remaining filled crack. The curing includes applying an energy source has described herein to cure the material. Next the crack is filled or partially with the energy curable material it is cured with an energy source described herein. This filling process and curing may be repeated. Optionally and/or alternatively, the surface can be leveled with a mechanical grinding techniques as known in the art, if required.

One embodiment is directed towards a method of using the energy curable material as a chemically resistant non-permeable protective layer or coating. The chemically resistant coating may be resistant to acid of less than 0 pH, 1 pH, 2 pH, 3 pH, 4 pH, 5 pH and higher. In addition, it is believed the coating is also resistant to a higher alkalinity, e.g., 6 pH to about 14 pH. Therefore, the coating will withstand harsh and destructive elements, e.g., sea water, steam, non-diluted muriatic acid, and the like. The protective coating may be formed on the desired substrate or material by applying the energy curable material to the material or substrate by any conventional technique, e.g., dipping, encapsulation, spray, paint brush, roller, combinations of the same or the like, to predetermined thickness. In a preferred embodiment, the thickness of the wet coating is in a range from about 2 mils to about 5 mils. Next, an energy source as described herein is applied to cure the material. Optionally and/or alternatively, the energy source may be pulsed, ramped non-linearly, ramped linearly or combination as described herein.

One embodiment is directed towards a method of manufacturing a premanufactured panel for an aerospace vehicle or application, e.g., decorative cabinets, walls, prefabricated panels and other materials. In this embodiment, a wood veneer is adhered to an aerospace substrate, e.g., honeycomb made of alloy, composite or combination of the same. The wood veneer may have one or more surfaces treated with a fire retardant. In one embodiment the veneer is not treated with a fire retardant as the energy curable material described herein. The adhesive may include adhesives as known in the art, e.g., 3M Hi-Strength 90 contact adhesive.

Optionally and/or alternatively, the veneer does not include a stain, but is a natural wood veneer, e.g., bird's eye maple. The method includes applying the energy curable material with a pigment, e.g., stain as a liquid or powder, to the desired tone, to one or more surfaces of the veneer. Optionally, the veneer may be entirely encapsulated with the energy curable material. The stain colors or darkens the appearance of the veneer. Next, an energy source is applied to the coating at a surface power density in range from about 3 mW/cm²to about 400 mW/cm²or greater to cure the applied material. Additional layers and curing is done until a desired thickness is reached.

Pigments can also create a translucent stain or toner and to create a specific finish appearance and pattern on stain-grade wood and solid colored substrates. The coating serves at least four simultaneous purposes including a stain, a fire-retardant, optionally an insulator, and a protective or a sealing coating in one process step, thereby, reducing processing steps and overall cost of forming the aircraft panel. The coating may be configured to any sheen gloss, semi-gloss, satin, flat, and egg shell. Optionally, the material in the initial coating, i.e., directly adjacent to the veneer, may be allowed to penetrate the veneer using a dwell time of 30 seconds to about 60minutes or more in an uncured state prior to curing with energy source. This dwell time allows the material to penetrate into the veneer by absorbing into the body of the veneer, e.g., pores, cracks, micro-cracks. Optionally and/or alternatively, heat can be applied to the material during the dwell time step or before the coating step with a heat source, e.g., heat gun or other conventional heating source. The heat allows moisture or VOC material in the veneer to be released.

One embodiment is directed towards a method of manufacturing a composite structure, e.g., a frame, fabricated by initially forming a stack of composite material herein in predetermined shape or in a mold. The energy curable material is applied to the material to saturate the material and an energy source as described herein to cure the material. Optionally and/or alternatively, the material may be further annealing in a furnace for a predetermined time and repeated.

In one embodiment, the composite material may include a semi-synthetic fiber, a cellulose fiber, a fiberglass fiber, a carbon fiber, synthetic fiber, a metallic fiber, a silicon carbide fiber, a mineral fiber, polymer fiber, a microfiber and combinations of the same.

One embodiment is directed towards forming an annular aircraft window frame including forming a stack of fibrous layer or composite material (described herein) impregnated or soaked with a VOC free low radiant flux UV material as described herein in an annular pattern. Forming an annular metal trim conforming with said annular pattern, trapping said trim in a lower transparent mold having a lower mold channel, trapping said stacked layers atop said trim in said lower transparent mold channel, and pressing an upper mold atop said stacked layers for compression applying the ultraviolent energy source in a range from about 360 nm to about 420 nm at a surface power density as described herein. Other energies as described herein may be utilized.

Optionally, and/or alternatively, the molds used in one or more embodiments may include a transparent mold with or without transparent vacuum bags for forming composites. The molds may include an integrated energy, e.g., embedded light emitting diodes, or any external energy source. The formed material may also be heated and/or cooled as described herein. Moreover, any composite part, coating or repaired may performed with the energy curable material described herein with the process as described with reference to U.S. patent application Ser. No. 15/593,985, which is hereby incorporated by reference for those purposes.

One embodiment is directed towards manufacturing a bathware by replacing the porcelain over steel bathware or glazed bathware with the energy curable material as described herein. The material is cured with an energy source as described herein. As discussed herein several layers with or without composite materials may be built up and cured. Optionally and/or alternatively, the bath ware may be created with one or more a mold, mold injection using the energy curable material. The pigments and additional decorative components may be used.

One embodiment is directed towards bonding of two or more materials, e.g., securing the windings over the guide to the rod on a fishing rod, securing windings on a fishing fly, securing electrical windings on motors, or any other process where the materials are desired to be bonded. In this embodiment, the materials to be bonded are coated or covered with the energy curable material. Next, energy from an energy source as described herein is applied to cure the material. These steps can be repeated until can be repeated until the desired thickness is achieved. The applied material is done with a sufficient quantity to cover the materials to be bonded, however, when bonding delicate materials, only small amounts of the energy curable material is required to secure them together until either a thicker layer or multiple layers are applied in a buildup process.

In a preferred embodiment, surface preparation of any surface being treated with the energy curable is done to ensure the surfaces of the materials to be bonded are clean (free of waxes, greases, oils or other contaminants) and dried. Optionally and/or alternatively, the surface preparation includes roughening the surface, e.g., with sandpaper or other mechanical mechanisms, file, grinder, and the like, to provide a roughened attachment point to allow for enhanced adhesion of the cured material.

One embodiment is directed towards an insulator coating for electrical applications. The energy curable is used to cover wires, e.g., bare wires, or other electrical components to any thickness as described herein by applying the material to a desired thickness, curing the material with an energy source as described herein. The cured material is an electrical insulator.

In one embodiment, an anti-tampering coating or junction is formed. This method may be useful for indicating a break in safety protocols requiring the physical security of an object within a storage container or device. The energy curable material is used to cover or create anti-tampering junction to any thickness as described herein by applying the material to a desired thickness, curing the material with an energy source described herein and repeating, if necessary. The cured material is now an anti-tampering junction, so one would know if the junction is open or broken. Of course, pigments and other additives may be included as described herein.

In one embodiment, the energy curable composition is configured as a clear sprayable formulation configures as a low viscosity formulation that can be sprayed onto a substrate with a conventional sprayer. Table 1 shows both a premium energy curable composition and an economy energy curable composition. The premium version would be expected to exhibit higher modulus than the economy version due to the use of SR368D. The economy version is less expensive due to the use of increased amounts of TPGDA and no SR368D. Each of the versions can be adjusted with one or more of a surface additive to reduce surface tension as described herein, e.g., 0-10% by weight of total composition, one or more performance additives as described herein, e.g., 0-20% by weight of total composition, a glass/silica fillers as described herein and optional pigments. Optionally and/or alternately, the pigments may include a matting agent to adjust the sheen or gloss, e.g., matte finish, semi-gloss finish, gloss finish, satin finish, egg shell finish and the like.

One embodiment, is directed towards energy curable material be applied to any material, e.g., composite material, to pre-impregnated. For example, a pre-impregnated composite material in the form a pre-impregnated sheets or rolls may be packed in a non-UV energy transparent material as a prepackage for future use. To use a user removes the pre-impregnated materials and cures with an energy source described herein.

TABLE 1

Sprayable Energy Curable Composition.

Premium Sprayable
Economy Sprayable

SR368D
59.41%
TPGDA
83.72%

PETMP
19.80%
PETMP
14.77%

TPO
0.79%
TPO
1.48%

HQ
0.06%
Q1301
0.03%

MEHQ
0.06%

TBC
0.06%

In one embodiment, the energy curable composition is a clearcoat composition as described Table 2. The composition of Table 2 can be adjusted with one or more of a surface additive to reduce surface tension as described herein, e.g., 0-10% by weight of total composition, one or more performance additives as described herein, e.g., 0-20% by weight of total composition, a glass/silica fillers as described herein and optional pigments. Optionally and/or alternately, the pigments may include a matting agent to adjust the sheen or gloss, e.g., matte finish, semi-gloss finish, gloss finish, satin finish, egg shell finish and the like. This composition can be cured with an energy source as described herein.

TABLE 2

Clearcoat Energy

Curable Composition.

TPGDA
24.72%

TMPEO3TA
57.68%

PETMP
14.54%

TPO-L
2.91%

HQ
0.05%

MEHQ
0.05%

TBC
0.05%

In one embodiment, the energy curable composition is a clearcoat composition as described Table 3. The energy curable composition of Table 3 can be adjusted with one or more of a surface additive to reduce surface tension as described herein, e.g., 0-10% by weight of total composition, one or more performance additives as described herein, e.g., 0-20% by weight of total composition, a glass/silica fillers as described herein and optional pigments. Optionally and/or alternately, the pigments may include a matting agent to adjust the sheen or gloss, e.g., matte finish, semi-gloss finish, gloss finish, satin finish, eggshell finish and the like. This composition can be cured with an energy source as described herein.

TABLE 3

Sprayable Energy

Curable Composition.

Photomer 6008
14.54%

TMPE03TA
67.87%

PETMP
14.54%

TPO-L
2.91%

HQ
0.05%

MEHQ
0.05%

TBC
0.05%

In one embodiment, the energy curable composition of Table 4 is thicker formulation that would be used to laminate composite materials, e.g., for use in applications such as making bathtubs or to laminate a carbon fiber cloth for use in applications such as airplane composites. Optionally and/or alternatively, a Photomer 6008 can be used instead of PE210. The compositions in Table 4 can be adjusted with one or more of a surface additive to reduce surface tension as described herein, e.g., 0-10% by weight of total composition, one or more performance additives as described herein, e.g., 0-20% by weight of total composition, a glass/silica fillers as described herein and optional pigments. Optionally and/or alternately, the pigments may include a matting agent to adjust the sheen or gloss, e.g., matte finish, semi-gloss finish, gloss finish, satin finish, eggshell finish and the like. This composition can be cured with an energy source as described herein.

TABLE 4

Laminating Energy

Curable Composition.

TPGDA
46.05%

PETMP
8.12%

TPO
0.81%

Q1301
0.02%

PE210
45%

(Bisphenol A

epoxy acrylate)

In one embodiment, the energy curable composition is a paste, e.g., knife grade paste, with compositions shown in Table 5 and Table 6. These formulations have been filled/compounded with silica particles to increase viscosity so that it has consistency of a paste and can be spread and shaped onto substrates with a “knife” blade. The premium version would be expected to exhibit higher modulus than the economy version due to the use of SR368D. The economy version is less expensive due to the use of increased amounts of TPGDA and no SR368D. The formulations in Tables 5 and 6 are clear.

TABLE 5

Paste Energy Curable Compositions.

Premium Paste
Economy Paste

SR368D
68.57%
TPGDA
77.61%

PETMP
22.86%
PETMP
13.69%

TPO
1.00%
TPO
1.37%

HQ
0.10%
Q1301
0.03%

MEHQ
0.10%
Aerosil 200
7.3%

TBC
0.10%

Aerosil 200
7.28%

TABLE 6

Paste Energy Curable Composition.

TMPEO3TA
73.82%

PETMP
13.03%

TPO-L
2.61%

HQ
0.04%

MEHQ
0.04%

TBC
0.04%

Aerosil 200
10.42%

In one embodiment, the energy curable composition is a paste, e.g., knife grade paste has a color pigment added of titanium dioxide to make it a white paste. Any pigment can be added as described herein. The compositions are Table 7 and Table 8. These formulations have been filled/compounded with silica particles to increase viscosity so that it has consistency of a paste and can be spread and shaped onto substrates with a “knife” blade. The premium version would be expected to exhibit higher modulus than the economy version due to the use of SR368D. The economy version is less expensive due to the use of increased amounts of TPGDA and no SR368D. The formulations in Tables 5 and 6 are clear.

TABLE 7

Pigmented Paste Energy Curable Composition.

Premium Paste
Economy Paste

SR368D
68.57%
TPGDA
77.61%

PETMP
22.86%
PETMP
13.69%

TPO
1.00%
TPO
1.37%

HQ
0.10%
Ql301
0.03%

MEEHQ
0.10%
Aerosil 200
7.3%

TBC
0.10%
White (TiO2)
3%

Aerosil 200
7.28%

White (TiO2)
3%

TABLE 8

Pigmented Paste Energy Curable Composition.

TMPEO3TA
73.82%

PETMP
13.03%

TPO-L
2.61%

HQ
0.04%

MEHQ
0.04%

TBC
0.04%

Aerosil 200
10.42%

White
2.54%

In embodiments herein and in Tables 1-8 and Examples the chemical names are disclosed here in also some abbreviations are listed in Table 9 for convenience.

TABLE 9

Chemical Names.

Product

CAS

Name
Chemical Makeup
Number
Type

SR368D
Mixture of tris
15625-89-5
Acrylate

(2-hydroxy ethyl)
40220-08-4
monomer/

isocyanurate triacrylate

oligomer

and trimethylolpropane

triacrylate

TPGDA
Tripropyleneglycol
42978-66-5
Acrylate

diacrylate

monomer/

oligomer

TMPEO3TA
Ethoxylated (3)
28961-43-5
Acrylate

trimethylolpropane

monomer/

triacrylate

oligomer

Photomer
aliphatic urethane
Proprietary
Acrylate

6008
triacrylate

oligomer

PETMP
Pentaerythritol tetra(3-
7575-23-7
Thiol

mercaptopropionate)

monomer/

oligomer

TPO
Diphenyl(2,4,6-
75980-60-8
Photoinitiator

trimethylbenzoyl)phosphine

oxide

TPO-L
ethyl(2,4,6-
84434-11-7
Photoinitiator

trimethylbenzoyl)-

phenyl

phosphinate

HQ
Hydroquinone
123-31-9
Radical inhibitor

MEHQ
4-methoxyphenol
150-76-5
Radical inhibitor

TBC
4-tert-butylcatechol
98-29-3
Radical inhibitor

Ql301
Aluminum n-
15305-07-4
Radical inhibitor

nitrosophenylhydroxylamine

IPA
Isopropanol
67-63-0
Solvent/diluent

In embodiments herein and in Tables 1-8 and Examples the chemical names are disclosed here in also some abbreviations are listed in Table 9 for convenience.

Certain non-limiting examples of mixing the enhanced fire retardant formulation with the non-enhanced fire retardant energy curable formulation can be done in-situ, prior to applying on a substrate or a combination of the same at various mixing ratios. By way of example an in-situ application can include applying an enhanced fire retardant formulation at a first thickness and then applying a non-enhanced fire retardant VOC free energy curable composition, e.g., low radiant flux curable formulation, at a second thickness to a substrate followed by curing the mixture with the application of the radiation source. The order of apply non-enhanced fire retardant VOC free low radiant flux curable formulation and the enhanced fire retardant VOC free low radiant flux curable formulation can vary or multiple applications can be done prior to curing the radiation sources. The first and second thickness may a thickness in a range from 0.0001 inch to about 1 inch or more.

In another non-limiting embodiment, Part 1 and Part 2 are applied in-situ, mixed or a combination. In this embodiment, Part 1 is the enhanced fire retardant VOC free low radiant flux curable formulation and Part 2 is the non-enhanced fire retardant VOC free low radiant flux curable formulation. When applying or mixing the ratios may be any of the following: (1:1) Part 1=100%, Part 2=100%; (2:1) Part 1=100%, Part 2=50%; (3:1) Part 1=100%, Part 2=33%; (4:1) Part 1=100%, Part 2=25%; (5:1) Part 1=100%, Part 2=20%; (6:1) ratio; (7:1) ratio; (8:1) ratio; (9:1) ratio; and (10:1) ratio of course, other ratios or sub-ratios and combinations may also be utilized.

In yet another embodiment, a first layer of non-enhanced fire retardant VOC free low radiant flux curable formulation was applied and not cured and a second layer of enhanced fire retardant VOC free low radiant flux curable formulation was applied and the two layers were cured simultaneously or substantially simultaneously.

In still yet another embodiment, a first layer of enhanced fire retardant VOC free low radiant flux curable formulation was applied and cured and a second layer of non-enhanced fire retardant VOC free low radiant flux curable formulation was applied and cured. dwell prior to curing for about thirty minutes

EXAMPLES

The following examples set forth preferred methods in accordance with the invention. It is to be understood, however, that these examples are provided by way of illustration and nothing therein should be taken as a limitation upon the overall scope of the invention.

Example 1

In this Example 1 an enhanced fire retardant VOC free low radiant flux radiation curable composition was utilized. The enhanced fire retardant composition coated veneer was compared to a non-enhanced VOC free low radiant flux radiation curable composition. More specifically, samples for flame testing were made by coating birch veneer purchased from Home Depot with the enhanced fire retardant composition.

The samples were sprayed using a badger gravity fed sprayer (the ones used for art) to a thickness of about 3-5 mils. The first coating as shown in Table 1 was allowed to dwell prior to curing for about thirty minutes, however, the other coats were simply applied and cured with little or no dwell time. Next, the samples were cured with an energy source by applying a radiation curing of about 2 minutes with an energy at a surface of the coating of about 5 mW/cm2or less with a UV LED energy source having a wavelength in a range from about 360 nm to about 420 nm.

After the first coat, the samples were sanded and two additional layers of the control formulation sprayed and cured without sanding. Each sample was placed flat about 3/4 inch from the tip of a candle flame and held there until it caught fire or for up to 3 minutes if it did not catch fire. Table 1 contains coating information and Table 2 contains the flame results. Table 3 contains pictures of each specimen and burn diameters.

Formulation A, which is a non-enhanced VOC free low radiant flux radiation curable composition used in this Example as part of the control. Was made as follows:

- 1. Weigh out inhibitors, HQ, MEHQ, TBC, and photo initiator, TPO
- 2. Add TMPEO3 TA and TPGDA
- 3. Mix until solids are dissolved

Wt.

Compound
CAS #
Supplier
Percent

TMPEO3TA
28961-66-5
IGM
25.5%

TPGDA
42978-66
IGM
59.5%

TPO
75980-60-5
IGM
3%

HQ
123-31-9
Aldrich
0.05%

MEHQ
150-76c5
Aldrich
0.05%

TBC
98-29-3
Aldrich
0.05%

- 4. Add PETMP and cover with foil

Wt.

Compound
CAS #
Supplier
Percent

PETMP
7575-23-7
Evens
15%

Chemical

- 5. Mix until miscible
- 6. Optionally Record viscosity

Formulation B-Enhanced Fire-retardant Formulation [FR]

Formulation B-Enhanced Fire-retardant Formulation [FR] was made by adding the fire retardant component as a performance additive as follows:

- 1. Weigh out inhibitors, HQ, MEHQ, TBC, and photo initiator, TPO-L
- 2. Add TMPEO3TA

Wt.

Compound
CAS#
Percent

TPGDA
42978-66
47.2%

TPO-L
75980-60-5
5.6%

SC1400A
Prop
47.2%

- 3. Cover and mix until all solids are miscible

The substrates were coated as shown in Table 10 and tested as shown in Table 11.

TABLE 10

Coatings for Flame Testing.

Control
FR

Coat 1
Formulation
Formulation B-

A-Non-
Enhanced FR

enhanced FR
Dwell time of

Dwell time of
about 30

about 30
minutes prior to

minutes prior
curing

to curing

Coat 2
Formulation
Formulation

A-Non-
A-Non-enhanced

enhanced FR
FR

Coat 3
Formulation
Formulation

A-Non-
A-Non-enhanced

enhanced FR
FR

The cured coating was tested as described herein as shown in Table 12.

TABLE 11

Flame Testing Results-Time to Ignition.

Samples tested for >3 minutes did not catch fire.

Run
Control
FR

Sample 1
40 s
>3 min

Sample 2
>3 min
>3 min

Sample 3
30 s
>3 min

Sample 4
40 s
80 s

Sample 5
50 s
>3 min

The results of the testing of Table 12 were measured to obtain an approximate burn diameter as shown in Table 13.

TABLE 12

Flame Testing Results.

Burn Diameter

Sample 1-
1.4 cm

Control

Sample 2-
1.8 cm

Control

Sample 3-
1.5 cm

Control

Sample 4-
1.8 cm

Control

Sample 5-
1.5 cm

Control

Sample 1-
4.5 cm

FR

Sample 2-
3.8 cm

FR

Sample 3-
3.7 cm

FR

Sample 4-
2.5 cm

FR

Sample 5-
3.4 cm

FR

Example 2

This Example 2 is directed towards comparing a VOC free low radiant flux radiation curable composition without a surface additive (“Formulation A”) to reduce surface tension to one with a surface additive to reduce surface tension (“Formulation C”) configured to be utilized on substrates that have impurities, e.g., oils, contaminants, other contaminates, in order to create smooth appearance without the need for further polishing or minimal buffing.

Formulation C was made as follows:

- 1. Weigh out inhibitors, HQ, MEHQ, TBC, and Photo Initiator, TPO-L
- 2. Add TMPEO3TA and TPGDA and BYK-333
- 3. Mix until solids are dissolved

Wt.

Compound
CAS #
Percent

TMPEO₃TA
28961-66-5
25.5%

TPGDA
42978-66
59.5%

TPO-L
75980-60-5
3%

BYK-333
Prop
0.3%

HQ
123-31-9
0.05%

MEHQ
150-76-5
0.05%

TBC
98-29-3
0.05%

4. Add PETMP and cover with foil

Wt.

Compound
CAS #
Percent

PETMP
7575-23-7
15%

5. Mix until miscible

6. Optionally Record viscosity

In Example 2, the formulation was made by two raw untreated veneer substrates were coated with a conventional wood stain on surface. The stain was a conventional wood stain that included volatile organic compounds and other contaminants configured with a fire retardant. These stained veneers were allowed to air dry for sixty minutes. Next both stained veneers were bonded to a larger base substrate by applying a 3M™M Hi-Strength 90 Spray Adhesive to the larger base substrate and an unstained surface of each veneer. FIG. 1 illustrates Example 2 having veneer A and veneer B attached to a substrate. Referring to FIG. 1, a stained veneer A 102 and stained veneer B 104 were attached to a substrate 106 prior to coating with an adhesive as described herein.

Next, at about 82 degree in the spray booth, Formulation A was applied to a first veneer, veneer A 102 and Formulation C was applied to a second veneer, veneer B 104 to a thickness of about 2 mils to about 5 mils. Each of the formulations were applied with a HVLP Jaguar SPP gravity feed sprayer. The applied coatings were allowed to dwell for about 5 minutes prior to applying a radiation curing of about 2 minutes at an energy at a surface of the coating of about 5 mW/cm²or less with a UV LED energy source having a wavelength in a range from about 360 nm to about 420 nm. Next, the surface was sanded with a 320 grit pad with an electric orbital sander disc for about 1 minute or less to remove any glossy features and the process was repeated five additional times.

FIG. 2 illustrates veneer A with a cured coating. FIG. 3 illustrates veneer B with a cured coating.

Referring to FIG. 2, illustrating veneer A 102 with a cured coating 202 to it was observed in this process that the Veneer A with a cured coating 202 coating had imperfections 204 including one or more of bumps, air bubbles, fish eyes and combinations of the same after each cured coating. As more layers were built up and cured the imperfections 204 were decreased, but still present. Also, with a final polish and sanding was required to remove the imperfections. At least some of these imperfections 204 are believed to be due to the impurities in the stain that was used, e.g., VOCs and other contaminants. Now referring to FIG. 3, showing veneer B 104 the cured coating 302 included much less or no imperfections and included a glassy finish 304. In addition, the final coating would require no or minimal polishing thereby saving labor costs and material, i.e., material that would have to be removed. The final coated and cured products are shown in FIG. 2 (Veneer A) and FIG. 3 (Veneer B). Again, comparing the products of FIGS. 2 and 3 it shows more work would be required to achieve a desired finish with FIG. 2 vs. FIG. 3. That is, FIG. 2 shows significant number of imperfections 204 remaining after curing while FIG. 3 shows none.

Example 3

Example 3 illustrates other formulations of a VOC free low radiant flux radiation curable composition used having a matte finish. Was made as follows:

- 1. Weigh out inhibitors, HQ, MEHQ, TBC, and PI, TPO
- 2. Add TMPEO3TA and TPGDA
- 3. Mix until solids are dissolved

Wt.

Compound
CAS #
Percent

TMPEO3TA
28961-66-5
25.5%

TPGDA
42978-66
59.5%

TPO
75980-60-5
3%

HQ
123-31-9
0.05%

MEHQ
150-76c5
0.05%

TBC
98-29-3
0.05%

- 4. Add PETMP and cover with foil

Wt.

Compound
CAS #
Percent

PETMP
7575-23-7
15%

- 5. Mix until miscible
- 6. Optionally Record viscosity
- 7. Carefully pour formulation for steps 1-5 over a powder.

Wt.

Compound
CAS #
Percent

Acematt 3600

7.4%

Formulation

192.6

from steps

1-5

- 8. Cover and begin mixing. Slowly ramp speed until all powder is incorporated. Mix until all components are miscible.
- 9. Bottle

Example 4

Example 4 illustrates other formulations of a VOC free low radiant flux radiation curable composition used having a high viscosity as a knife grade paste. Was made by mixing the following:

- 1. Weigh out inhibitors, HQ, MEHQ., TBC, and photo initiator, TPO
- 2. Add TMPEO3TA and TPGDA
- 3. Mix until solids are dissolved

Compound
CAS #
Wt. Percent

TMPEO₃TA
28961-66-5
81.6%

TPO
75980-60-5
2.88%

HQ
123-31-9
0.05%

MEHQ
150-76c5
0.05%

TBC
98-29-3
0.05%

- 4. Add PETMP and cover with foil

Compound
CAS #
Supplier
Wt. Percent

PETMP
7575-23-7
Evens
14.4%

Chemical

- 5. Mix until miscible
- 6. Optionally add sheening agent of Acematt 3600 and mix until miscible for a matte finish.

Compound
CAS #
Supplier
Wt. Percent

Acematt 3600

Evonik
4%

Example 5

Example 5 illustrates other formulations of a VOC free low radiant flux radiation curable composition used as a laminating resin. Was made as follows:

- 1. Weigh out inhibitors, HQ, MEHQ, TBC, and photo initiator, TPO
- 2. Add TMPEO3TA

Compound
CAS #
Wt. Percent

TMPEO3 TA
28961-66-5
70%

TPO-L
75980-60-5
3%

HQ
123-31-9
0.05%

MEHQ
150-76c5
0.05%

TBC
98-29-3
0.05%

- 3. Cover and mix until all solids are dissolved
- 4. Add Photomer 6008.

Compound
CAS #
Wt. Percent

Photomer 6008
Prop
15%

- 5. Cover and mix until all components are miscible
- 6. Add PETMP and cover with foil.

Compound
CAS #
Wt. Percent

PETMP
7575-23-7
15%

- 7. Cover and mix until all components are miscible

Example 6

Example 6 illustrates other energy curable compositions and energy and times to cure to a tack free coating. In this example, three formulations were made including

Formulation 6A, 6B and 6C were made.

Formulation 6A was made as follows:

- 1. Weigh out inhibitors, HQ, MEHQ, TBC, and photo initiator, TPO
- 2. Add TMPEO3 TA and TPDGDA
- 3. Mix until solids are dissolved

Compound
CAS #
Wt. Percent

TMPEO₃TA
28961-66-5
25.5%

TPGDA
42978-66
59.5%

TPO
75980-60-5
3%

HQ
123-31-9
0.05%

MEHQ
150-76-5
0.05%

TBC
98-29-3
0.05%

- 4. Add PETMP and cover with foil

Compound
CAS #
Wt. Percent

PETMP
7575-23-7
15%

- 5. Mix until miscible
- 6. Record viscosity

Formulation 6B was made as follows:

- 1. Weigh out inhibitors, HQ, MEHQ, TBC, and photo initiator, TPO
- 2. Add TMPEO3TA
- 3. Mix until solids are dissolved

Compound
CAS #
Wt. Percent

TMPEO₃TA
28961-66-5
85.5%

TPO-L
75980-60-5
2%

HQ
123-31-9
0.05%

MEHQ
150-76-5
0.05%

TBC
98-29-3
0.05%

- 4. Add PETMP and cover with foil
- 5. Mix until

Compound
CAS #
Wt. Percent

PETMP
7575-23-7
15%

- 6. Measure out 70 grams of material into a speedmixer cup
- 7. Add 2.1 g amount of “Aerosil 200 add 1”. Mix on 10-13 rpm
- 8. Add 2.1 g amount of “Aerosil 200 add 2”. Mix on 13-16 rpm
- 9. Add 2.1 g amount of “Aerosil 200 add 3”. Mix on 20-25 rpm
- 10. Add 2.1 g amount of “Aerosil 200 add 4”. Mix on 25-36 rpm
- 11. Allow to cool to room temperature
- 12. Mix a final time at max speed
- 13. Add 26 g of paste to a 20cc syringe

Formulation 6C was made as follows:

- 1. Weigh out inhibitors, HQ, MEHQ, TBC, and photo initiator, TPO
- 2. Add TMPEO3TA

Compound
CAS #
Wt. Percent

TMPEO₃TA
28961-66-5
70%

TPO-L
75980-60-5
3%

HQ
123-31-9
0.05%

MEHQ
150-76-5
0.05%

TBC
98-29-3
0.05%

- 3. Cover and mix until all solids are dissolved
- 4. Add Photomer 6008

Compound
CAS #
Wt. Percent

Photomer 6008

15%

- 5. Cover and mix until all solids are dissolved
- 6. Add PETMP and cover with foil

Compound
CAS #
Wt. Percent

PETMP
7575-23-7
15%

- 7. Cover and mix until all components are miscible.
- 8. Record viscosity

Each formulation 6A, 6B, and 6C were tested with results shown in Table 14and drawn down on a glass microscope slide with an Accu Dyne #50 (127 μm) bar. The sample was irradiated under a 390-410 nm (Edison 150 watt) light at the designated intensity. The intensity was measured with an International Light Radiometer 1L1400 tack free was determined by pressing a fresh latex glove against the surface of the polymer with moderate pressure. If the polymer is marred in any way the surface is tacky. If no residue is observed on the glove and the surface is unmarred, then the surface is considered to be tack free.

TABLE 14

Results

Energy Curable
Energy Curable
Energy Curable

Composition 6A-
Composition 6B-
Composition 6C-

Intensity
Cure Time (s)
Cure Time(s)
Cure Time (s)

(mW/cm²)
to tack free
to tack free
to tack free

5
120
120
120

10
75
75
65

20
30
50
30

40
20
40
20

Example 7

This Example 7 illustrates creating an energy curable composition that is a clear sprayable formulation. The composition is VOC free and will cure tack free with non-yellowing upon application of UV light source with a sufficient energy for a sufficient time. In this example, the formulation was created by adding 100 grams of TMP (EO) 3TA was added to 8grams of 1-Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184) in a container and mixed with an overhead stirrer for approximately 45 minutes or until all of the Irgacure 184 was dissolved. Dissolving the Irgacure 184 may be sped up by the application of heat to the container by placing the container on a hot plate at temperature of approximately 60° C. The made composition was 92.6 weight percent % TMP (EO)3TA and 7.4 weight percent % Irg 184.

The formulation was then applied to a substrate to a thickness of approximately 25 um using a drawdown bar and irradiated with a 150 W Edison UV-LED (390-410 nm) light source for 1 minute. The light source even at the highest intensity (as close as possible to the light about 1 inch or less, >80 mW/cm