BR112019021114A2 - COMPOSITIONS AND ADHESIVE METHODS FOR COATING OBJECTS - Google Patents

Abstract

an adhesive composition comprising a core-coated vinyl ester and urethane acrylate, which is suitable to be applied to a rough or uneven surface of a substrate to make a smooth surface. the present adhesive composition is particularly suitable for coating large objects made by means of additive manufacturing to form molds or prototypes.

Description

COMPOSITIONS AND ADHESIVE METHODS FOR COATING OBJECTS

JOINT SEARCH AGREEMENT

[0001] Aspects of the present invention were made by or on behalf of the parties listed below in a joint research agreement. The joint research agreement was in effect before or on the date when aspects of the present invention were made and aspects of the present invention were made as a result of activities carried out under the scope of the joint research agreement. The parties to the joint research agreement are Polynt Composites USA Inc., Polynt Composites Canada Inc., and Tru-Design, LLC.

BACKGROUND OF THE INVENTION

[0002] The present application generally relates to an adhesive composition useful as a coating or sealant for objects. In particular, the present composition is useful as a coating or sealant for objects with a rough or uneven surface, such as objects made by additive manufacturing.

[0003] Additive manufacturing, also known as three-dimensional printing, has grown in popularity and is now used in a wide variety of industries for the manufacture of objects. However, objects made by additive manufacturing have a rough surface and are therefore not suitable for use in many intended applications, for example, as molds or prototypes. Therefore, there is a need for an improved composition and method to improve the surface of objects made through additive manufacturing.

[0004] Previous attempts to address the rough surface of these objects included grinding the object to create a smooth surface and then painting the object to render the final product. However, thturation of the object is time consuming, creates a large amount of dust which is often problematic due to its carbon or other fiber content and limits the usefulness of the additive manufacturing process for real world applications. In addition, paint failure is common due to the inability of the paint to withstand the expansion and contraction of

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2/38 object.

[0005] Existing coating compositions for objects made by means of additive manufacturing, particularly large objects, generally do not have sufficient adhesion to common substrates, such as acrylonitrile butadiene styrene (ABS), polyphenylene sulfide (PPS) and others. In addition, existing coating compositions fail due to expansion and / or contraction of the substrate under various conditions. Thus, there is a need for a coating composition that can sufficiently adhere to common substrates and Tenderize an object with a smooth surface.

[0006] Large objects manufactured by additive manufacturing have several other technical challenges, detailed in part by Sudbury et al., Int J Adv Manuf Technol. (September 29, 2016), which is incorporated by reference in its entirety. These challenges include, among others, grouping paint or adhesive sealant and cracking them. Therefore, there is a need for a coating composition that can overcome the known problems associated with large objects made by additive manufacturing.

[0007] The objects manufactured by additive manufacturing finished by known compositions and methods suffer from the lack of durability. Molds made of traditional materials can withstand tensile strengths greater than 10, greater than 50 or greater than 100. However, molds comprising objects made by additive manufacturing can only support strengths less than 5 or less than 10. Therefore, there is a need of a coating composition that can withstand mechanical forces associated with standard mold use.

[0008] Objects manufactured by additive manufacturing may undergo further processing to add parts to the objects. These objects are autoclaved under vacuum. The prior art compositions failed to withstand the temperature and pressure changes associated with the vacuum autoclave. Therefore, there is a need for a coating composition that can withstand changes in temperature and pressure associated with finishing objects made by additive manufacturing.

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SUMMARY

[0009] The present disclosure relates to a composition comprising a core-coated vinyl ester resin and a urethane acrylate. The vinyl ester resin of the core shell may comprise 25 to 95% of the total weight of the composition and / or contain polymer of the core shell with an average diameter of 50 to 350 nm. Urethane acrylate can comprise 2 to 25% of the total weight of the composition.

[0010] The present composition may optionally further comprise a monomer, one or more additives and / or one or more unsaturated polyester resins. A particularly suitable monomer is styrene or its derivative. Suitable additives include a crosslinking agent, curing agent, thixotropic agent, air release / wetting agent, coloring agent, air release, inorganic or organic filler, light filler, surfactant, inorganic or organic nanoparticles or combinations thereof.

[0011] The present composition can have a carbamate bond content of 0.1 to 10%; exhibits a heat deflection temperature greater than 140 ° F; and / or the composition can stretch more than 5%.

[0012] The present disclosure further relates to a polymer composite article, preferably produced by additive manufacturing, comprising a polymer body having a surface and an adhesive coating comprising core-coated vinyl ester resin or the current ester resin composition core coating vinyl and urethane acrylate. The polymer composite article is made of a substrate where the type of substrate can be acrylonitrile-butadiene-styrene, polyphenylene sulfide, polypenyl sulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid or combinations thereof. These types of substrate can be reinforced with materials including, but not limited to, glass fibers, carbon fibers, bamboo or combinations thereof.

[0013] When the adhesive coating is applied to the polymer composite article, it can be applied in a way that the composition has a

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4/38 average thickness greater than 0.08 inches on the substrate surface. Once cured, the adhesive coating (1) adheres to the substrate surface; (2) the bond strength between the adhesive coating and the substrate surface is greater than 300 psi; and / or (3) the adhesive coating, after curing, may have a finished surface profile of less than 0.10 mm.

[0014] The present disclosure further relates to a method of using the present composition to manufacture a polymer composite article, such as a mold or prototype, comprising (a) forming a substrate comprising a polymer body with a surface; (b) applying an adhesive coating to the surface of the polymer body, wherein the adhesive coating comprises core-coated vinyl ester resin; and (c) curing the adhesive coating applied in (b). The application step can be performed using a squeegee, roller, trowel, spatula, paint stick, brush or other mechanical resources. Alternatively, the application step can be carried out using a sprayer to spray the composition onto the object. The result of the application step can be a layer of adhesive coating with a thickness greater than 0.08 inches to achieve the desired properties.

[0015] In some cases, several applications of the adhesive coating are guaranteed. In these cases, the previous application of the adhesive coating must cool down to 10 ° F from the initial temperature of the substrate surface. Then, an additional application of the adhesive coating can be made over the previous application of the adhesive coating and allow curing.

BRIEF DESCRIPTION OF THE DRAWING

[0016] The present disclosure can be better understood from the detailed description below, when dealing with the attached drawing. Resources are not necessarily drawn to scale.

[0017] FIG. 1 illustrates the present composition applied to a surface of a substrate as an adhesive coating or sealant in a manner as disclosed herein to form a finished object.

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DETAILED DESCRIPTION

[0018] The present adhesive composition can be used as an adhesive composition that works to fill empty spaces of objects with a rough or uneven surface present on certain substrates. The present adhesive composition can also be used as a sealant capable of withstanding changes in temperature and pressure common to objects comprising certain substrates. Both objects can be created by an additive manufacturing process.

[0019] A composition and methods of use disclosed herein are designed for use with objects with a rough or uneven surface. As used herein, an object includes an article of manufacture, preferably a polymer composite article, and most preferably a polymer composite article made by means of additive manufacturing and, ideally, a polymer composite article made by means of fabrication of large-scale additive. In preferred modalities, the object can be a mold or prototype. Objects can comprise a wide range of polymeric substrates, including, but not limited to, acrylonitrile butadiene styrene (ABS), polyphenylene sulfide (PPS), polyphenyl sulfone (PPSU), polyethersulfone (PES), polyethylene terephthalate, polybutylene terephthalate, polylactic acid (PLA ) and the like. These substrates can optionally be reinforced with glass fibers, carbon fibers, bamboo or the like, or combinations thereof. One skilled in the art would appreciate that other similar substrates could be used with the present composition.

[0020] In the modalities, the present composition adheres to substrates with a surface profile in the range of 1.0 to 10 mm; alternatively, 2 to 7.5 mm; or alternatively 2.5 to 5.0 mm.

[0021] When the present composition is applied to objects with a rough or uneven surface such as an adhesive or sealant coating and allowed to cure, the result is an object that is impermeable or substantially impermeable to gas or liquid. In other words, the use of the present composition inhibits the entry of gas or liquid into the object's substrate.

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[0022] The present composition, when used as an adhesive coating or sealant, has been shown to withstand experimental and standard thermal cycles without showing the underlying defects on the substrate surface or losing the vacuum seal. Without being limited by any particular theory, it is believed that the ability to withstand these thermal changes without deformation is at least partially attributable to the elongation properties of the present composition.

[0023] In the modalities, the present composition, when used as an adhesive coating or sealant, also works to fill all common printing defects in objects made by means of additive manufacturing. A non-limiting list of common defects includes grooves, geometric imperfections, missing or broken granules, underfilling cavities, and surface contour / texture / resolution problems. As a result of this function, the use of the present composition results in objects with a smooth surface receptive to the final finish (for example, painting). These objects are ideal for use as molds or prototypes.

[0024] The present composition comprises a core-coated vinyl ester resin and a urethane acrylate. As used herein, a "core coated vinyl ester resin" means a vinyl ester resin and a core coating polymer, wherein a core coating polymer is dispersed throughout the vinyl ester resin. An exemplary vinyl ester is disclosed in WO1997 / 043339, which is incorporated herein by reference in its entirety. Such resins have also been referred to as "hardened vinyl ester resins". The best known and most used vinyl ester resin is produced from bisphenol-A diglycidyl ether (DGEBA) and methacrylic acid. Typically, an amine or triphenylphosphine salt is used to catalyze the reaction at a temperature of about 120 ° C for 4 to 5 hours. 90 to 95% of methacrylic acid reacts to form the vinyl ester. Styrene can be added to reduce viscosity during synthesis. Alternatively, the glycidyl metachlate can be reacted with a multifunctional phenol to form a vinyl ester resin.

[0025] Core coating polymers, which are dispersed in

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7/38 vinyl ester resins, in accordance with the present disclosure, are generally produced by controlled emulsion polymerization, during which the composition of the monomer feed is altered, in order to achieve a desired composition variation on the polymer structure of core coating. Although many core coating polymers with a variety of properties are available, core coating polymers suitable for use in the present composition typically have a core that is rubberized under environmental conditions, being produced by polymerizing monomers such as butadiene and alkyl acrylates . It will be understood that "rubberized under environmental conditions" means that the core of the core coating polymer has a Tg below room temperature. Preferred core coating polymers include, but are not limited to, polymerized versions of: butadiene; butadiene and styrene; butadiene, methyl methacrylate and styrene; butadiene, alkyl methacrylate and alkyl acrylate; butadiene, styrene, alkyl acrylate, alkyl methacrylate and methacrylic acid; butadiene, styrene, alkyl acrylate, alkyl methacrylate, methacrylic acid and low molecular weight polyethylene (as a flow modifier); butyl acrylate and methyl methacrylate; alkyl methacrylate, butadiene and styrene; alkyl acrylate, alkyl methacrylate and glycidyl methacrylate; and alkylacrylate and alkylmethacrylate. The core coating polymer can comprise an average diameter of 50 to 350 nm; alternatively, 100 to 300 nm; alternatively, 150 to 250 nm; alternatively, about 200 nm; or alternatively, 200 nm. Particularly preferred core coating polymers for use in the present composition are core coating polymers that incorporate butadiene as a core component. A preferred coating component is poly (methyl methacrylate) (PMMA). The core coating polymer may be amine-terminated butadiene nitrile rubber (ATBN) nanoparticles. A suitable core coating polymer is the polybutadiene core with poly (co-styrene methyl methyl methacrylate) coating. The core coating polymer can be optionally disposed within a resin

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8/38 carrier. The carrier resin may be a general purpose bisphenol epoxy resin or derivatives known to those skilled in the art. For example, a preferred carrier resin is a bisphenol A diglycidyl ether and its extended versions. The carrier resin can be a diepoxy resin, for example, Novalac.

[0026] In the embodiments, the main coating vinyl ester resin comprises about 25 to about 95%; alternatively, 25 to 95%; alternatively, 50 to 95%; alternatively, 60 to 95%; or alternatively 75 to 95% of the total weight of the present composition.

[0027] As used here, "urethane acrylate" means a diisocyanate reaction product, a functional OH molecule with olefinic double bond and optional material containing mono-, di- or multifunctional OH. An example of urethane acrylate for use in the present composition is disclosed in US Patent Nos. 4,485,226 and 4,507,458, which are incorporated herein by reference in their entirety. As used here, "diisocyanates" means any type of aromatic, aliphatic, alicyclic and aromatic-aliphatic polyisocyanates, two or more isocyanate groups in each molecule; including dimers and trimers. Examples of aromatic polyisocyanates include diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI). Examples of aliphatic polyisocyanates include hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). The "functional olefinic OH-molecule -OH" can include partial esters of polyhydric alcohols with acrylic acid or methacrylic acid, such as, for example, 1,2- or 1-monoacrylate or ethylene glycol monoacrylate or monomethylacrylate, 1,4-butanediol monoacrylate or monomethacrylate, 1,6-hexanediol monoacrylate or monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane diacrylate, glycerol diacrylate, pentaerythritol-and-mono-acrylate and mono-acrylate (mono-acrylate) methylolachlamide) -ethylene glycol ethers, propylene glycol, butanediol, hexanediol and neopentyl glycol. The “mono, di or multifunctional OH-containing material” may include polyfunctional alcohols, such as 2 to 8 carbon atoms, for example, ethylene glycol, propanedio, butanedio,

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9/38 pentanediools, hexanediois, triois, such as, for example, glycerol, trimethylolpropane and hexanothiois, pentaerythritol and the like; or polyether polyols prepared by reacting 1 molecule of alcohol with 1 to 50, preferably 15 to 30 molecules, molecules of ethylene oxide or propylene oxide. Polyester polyols can include the polycondensation reaction product of polybasic acids, such as adipic acid, succinic acid, azelaic acid, sebatic acid, phthalic acid, isophthalic acid and terephthalic acid, with polyhydric alcohols such as 1,4-butanediol , 1,3butanediol, ethylene glycol, diethylene glycol, propylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,6-hexaneglycol and neopentyl glycol.

[0028] In the modalities, urethane acrylate has one or more of the following attributes: a carbamate bond content of 0.1 to 10%, alternatively, 0.5 to 5%, alternatively, 0.5 to 4%, or alternatively, 0.5 to 3%; a nominal molecular weight of 600 to 5000, preferably 1500 to 3000; viscosity of about 4000 cps at 60 ° C.

[0029] In the modalities, urethane acrylate comprises about 2 to about 25%; alternatively, 2 to 25%; or alternatively 5 to 20% of the total weight of the present composition.

[0030] The present composition may further comprise one or more additives selected from an air release / wetting agent, rheology modifier, thixotropic synergist, inhibitor, initiator, catalyst, surfactant, filler and paraffin wax. The present composition can comprise more than one additive of the same type (for example, one or more fillers) or a combination of additives of different types (for example, at least one catalyst and at least one surfactant).

[0031] When present, the one or more additives can comprise from about 0.1 to about 40%; alternatively 0.1 to 40%; alternatively, 0.1 to 20%; or alternatively, 0.1 to 15% of the total weight of the present composition.

[0032] The present composition can further comprise a monomer. Exemplary monomers include, but are not limited to, styrene, methyl methacrylate, vinyl toluene, hydroxymethylmetachlate, hydroxymethyl acrylate, hydroxyethyl

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10/38 methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, alpha methyl styrene and divinyl benzene. Other exemplary monomers include o-methyl styrene, m-methyl styrene, p-methyl styrene, methyl acrylate, t-butyl styrene, diallyl phthalate, trialyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate; ethoxylated trimethylolpropane triacrylate; glycerylpropoxy triacrylate; propylene glycol diacrylate; ethylene glycol diacrylate; ethylene glycol dimethacrylate; ethylene glycol diacrylate; tetraethylene glycol diacrylate; triethylene glycol dimethacrylate; tripropylene glycol dimethacrylate; polypropylene glycol diacrylate; polyethylene glycol dimeacrylate; butanediol diacrylate; butane-diol dimethacrylate; pentaerylitol triacrylate; pentaerythritol tetra-acrylate; ethoxylated bisphenol A diacrylate; hexane diol diacrylate; dipentaerythritol monohydroxypenta acrylate; neopentyl glycol diacrylate; neopentyl glycol dimethacrylate; and tris (2-hydroxyethyl) isocyanurate triacrylate. In preferred embodiments, the monomer is styrene or one of its derivatives.

[0033] The monomer can comprise 0.1 to about 40%; alternatively, 0.1 to 40%; alternatively, 0.1 to 30%; or alternatively 0.1 to 20% of the total weight of the present composition.

[0034] The present composition may comprise a composition of several parts, where each part is prepared separately and then combined to arrive at the present composition. In these embodiments, the present composition comprises a first part comprising the vinyl ester resin covering the core; and a second part comprising a urethane acrylate. The present composition may optionally further comprise a third part comprising a monomer as described herein.

[0035] The first part can comprise about 25 to about 95%; alternatively, 25 to 95%; alternatively, 30 to 95%; alternatively, 50 to 90%; alternatively, 55 to 85%; alternatively, 60 to 80%; alternatively, 65 to 75%; or alternatively, 70 to 75% of the total weight of the present composition.

[0036] The second part can comprise about 2 to about 25%; alternatively, 2 to 25%; alternatively, 5 to 20%; alternatively, 5 to 15%;

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11/38 or alternatively, 10 to 15% of the total weight of the present composition.

[0037] The third part can comprise about 1 to about 75%; alternatively, 1 to 75%; alternatively, 2 to 40%; alternatively, 10 to 30%; alternatively, 10 to 20%; or alternatively, 15 to 20% of the total weight of the present composition.

[0038] The first part may comprise a core-coated vinyl ester resin described here. The first part can comprise a reaction product of an epoxy resin and a methacrylic acid or derivative thereof, in which the core coating polymers are applied to the epoxy resin. The epoxy resin may comprise a liquid epoxy resin derived from bisphenol A / epichlorohydrin. For example, a suitable liquid epoxy resin derived from bisphenol A / epichlorohydrin is D.E.R. ™ 331 available from Dow (Midland, Ml 48674). Another suitable liquid epoxy resin derived from bisphenol A / epichlorohydrin is EPON ™ 828 resin available from Hexion Specialty Chemicals (Columbus, OH 43215). In the embodiments, the liquid epoxy resin derived from bisphenol A / epichlorohydrin is a resin with an epoxide equivalent weight (g / eq) ranging from 185-192, a viscosity at 25 ° C from 110 to 150P, a density at 25 ° C 9.7 Ibs / gal, a vapor pressure at 77 ° C of about 0.03 mm Hg, a refractive index at 25 ° C of about 1.5 and / or a specific heat of about 0.5 BTU / lb / ° F. In the embodiments, the liquid epoxy resin derived from bisphenol A / epichlorohydrin is a resin with an epoxide equivalent weight (g / eq) ranging from 182-192, a percentage of epoxide ranging from 22.4 to 23.6%, a content epoxide group ranging from 5200 to 5500, a viscosity ranging from 11000 to 14000 mPa-s and / or a density at 25 ° C of about 1.16 g / ml. In preferred embodiments, the epoxy resin is a mixture of two or more liquid epoxy resin derived from bisphenol A / epichlorohydrin described herein.

[0039] The epoxy resin can comprise about 10 to about 55%; alternatively, 10 to 40%; alternatively, 15 to 35%; alternatively, 20 to 30%; or alternatively, 25 to 30% of the total weight of the first part.

[00401A vinyl ester resin with a core coating resulting from the

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The first part can comprise about 60 to about 95%; alternatively, 60 to 95%; alternatively, 65 to 95%; alternatively, 70 to 95%; or, alternatively, 75 to 95% of the total weight of the first part.

[0041] In the modalities, the first part can also comprise a monomer described here, which can comprise about 10 to about 80%; alternatively, 10 to 70%; alternatively, 20 to 40%; or, alternatively, 25 to 35% of the total weight of the first part. In preferred embodiments, the monomer is styrene or one of its derivatives.

[0042] The first part may also comprise one or more additives. Particularly suitable additives are stabilizers that facilitate the service life or stability of the first part and / or, finally, the total current composition. A suitable additive for the first part is the hydroquinone available from SigmaAldrich Co., LLC (St. Louis, MO 63103). When present, hydroquinone comprises less than 1%; alternatively, less than 0.05%; alternatively, 0.01 to 0.05%; alternatively, about 0.03%; or, alternatively, 0.03% of the total weight of the first part. Another suitable additive for the first part is 4methoxyphenol available from Sigma-Aldrich Co., LLC (St. Louis, MO 63103). When present, 4-methoxyphenol comprises less than 0.1%; alternatively, less than 0.05%; alternatively, 0.001 to 0.015%; alternatively, about 0.01%; or, alternatively, 0.01% of the total weight of the first part. Another suitable additive for the first part is p-benzoquinone available from SigmaAldhch Co., LLC (St. Louis, MO 63103). When present, p-benzoquinone comprises less than 1%; alternatively, less than 0.5%; alternatively, 0.2 to 0.4% of the total weight of the first part. Another suitable additive for the first part is maleic anhydride available from Sigma-Aldrich Co., LLC (St. Louis, MO 63103). When present, maleic anhydride comprises less than 1%; alternatively, 0.2 to 0.6%; alternatively, 0.3 to 0.5% of the total weight of the first part. Another suitable additive for the first part is 2-hydroxyethylmetachlate available from Sigma-Aldrich Co., LLC (St. Louis, MO 63103). When present, 2-hydroxyethylmethacrylate comprises about 1 to about 10%;

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13/38 alternatively, 1 to 10%; alternatively, 2 to 8%; alternatively, 3 to 6%; alternatively, about 5%; or alternatively, 5% by weight of the total weight of the first part.

[0043] Urethane acrylate can comprise about 40 to about 90%; alternatively, 40 to 90%; alternatively, 50 to 90%; alternatively, 60 to 90%; or alternatively, 70 to 90% of the total weight of the second part.

[0044] The second part may also comprise one or more additives. A suitable additive for the second part is methylhydroquinone. When present, methyl hydroquinone can comprise 100 to 500 ppm; or alternatively, 300 to 400 ppm. A monomer can also be added to the second part. When present, the monomer can comprise 0.5 to 60%; alternatively, 5 to 40%; or, alternatively, 10 to 25% of the total weight of the second part.

[0045] In one embodiment, the present composition comprises the components listed in Table 1.

Table 1:

Component Composition Weight Percent Total Coating vinyl ester resin 25 - 95% core Urethane acrylate 2 - 25% Monomer 0 - 40% Additions 0 - 40%

[0046] The additives observed in Table 1 can be added directly to an individual component, as described in the multi-part disclosure or the total composition. In another embodiment, the present composition can comprise the components listed in Table 2.

Table 2:

Component Composition Weight Percent Total Coating vinyl ester resin 75 - 95%

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core Urethane acrylate 5 - 25% Styrene 0 - 20% Additions 0-10%

[0047] The additives observed in Table 2 can be added directly to an individual component, as described in the multi-part disclosure or the total composition.

[0048] In yet another embodiment, the present composition can comprise the components listed in Table 3.

Table 3:

Component Amount Composition of Tables 1 or 2 10 - 99.9% by weight of the total composition Monomer 0 - 90% by weight of the total composition Air release agent 0 - 5% by weight of the total composition Inhibitor 10-2000 ppm Catalyst 0.01 - 3% by weight of the total composition Co-catalyst 0-1% by weight of the total composition Bridge agent 0 - 5% by weight of the total composition Rheology modifier 0 - 5% by weight of the total composition Filling agent 0 - 80% by weight of the total composition Coloring Agent 0 - 25% by weight of the total composition

[0049] The core-coated vinyl ester resin or the first part can be made according to the following procedure. In a clean, dry glass reactor equipped with a stirrer, dry air spray and heating blanket, load the epoxy bisphenol A and the core coating polymer dispersed in epoxy and mix. The mixture is then heated to approximately 115 ° C. Tetramethylammonium chloride and bisphenol A are added slowly keeping the temperature between 115 and 120 ° C until the epoxy number is stable.

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Monomer, hydroquinone and 2, 4, 6- tri (dimethylaminomethyl) phenol can be added at this point and mixed. The methacrylic acid is then added gradually and mixed over a period of two hours maintaining the temperature at approximately 115 ° C until the acid value is stable. The mixture is then cooled to room temperature. The additives disclosed in this document can be added to the chilled mixture to form the first part.

[0050] The urethane achlate or the second part can be done according to the following procedure. In a clean, moisture-free glass reactor equipped with a sprinkler and dry air stirrer, add toluene diisocyanate and triphenylantimony to the reactor to start stirring. Then, start spraying dry air and add hydroxyethyl acrylate for a period of two hours, keeping the temperature below 130 ° F. The mixture is then maintained for 30 minutes at 125 ° F. Methylhydroquinone is then added and mixed. Then, the polyol is added gradually over a period of one hour at 130 ° F. When the isocyanate reaction is complete, add 100 ppm of methylhydroquinone and monomer and mix. The mixture is then cooled to room temperature. The additives disclosed in this document can be added to the chilled mixture to form the second part.

[0051] The present composition can be manufactured using a high shear mixer (for example, a helical mixer). In the embodiments, the vinyl ester resin of the core coating or the first part is added together with the urethane acrylate or the second part and mixed for approximately 3 minutes by means of a high shear mixer in a temperature range below 120 ° F. The monomer or third part and / or one or more additives are then added to the mixture and mixed to achieve the desired physical properties. In preferred embodiments, the first part and the second part are added and mixed for approximately three minutes through a high shear mixer in a temperature range below 65-85 ° F. Then, monomers and additives can be added to the mixture to obtain the ideal physical properties. For example, monomer and

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16/38 additives can be added until the present composition exhibits one or more of the following characteristics: viscosity of 10,000 to 30,000 cPs at 20 rpm; viscosity of 16,000 to 20,000 cPs at 20rpm; thixotropic index greater than 3; thixotropic index greater than 4; gel time of 6 to 10 minutes at room temperature; a density ranging from 0.50 to 1.0 g / cm ³ ; or a density ranging from 0.70 to 0.80 g / cm ³ . Additives particularly suitable for achieving these characteristics include an air / wetting agent, one or more rheology modifiers, thixotropic synergist, one or more inhibitors, one or more initiators, one or more catalysts, one or more surfactants, one or more more fillers, paraffin wax.

[0052] When present, the air release agent / wetting agent is selected from polyacchlate, silicone, mineral oil or combinations thereof. When present, the rheology modifier is selected from fumed silica; clay, particularly organo-treated clay; Castor oil; polyamides; and combinations thereof. When present, the catalyst is selected from cobalt naphthenate, cobalt octoate, cobalt hydroxide, potassium octoate, potassium naphthanate, manganese salts, iron salts, NN-dimethyl aniline, NN-dimethyl-p-toluidine . In preferred embodiments, the present composition uses a combination of two catalysts, described elsewhere in this document as a catalyst and co-catalyst. In preferred embodiments, one or more catalysts and co-catalysts are added to the present composition prior to application for the desired curing performance, depending on the intended use. When present, the inhibitor can be a chemical capable of prolonging the gel time and / or extending the useful life of the present composition. Exemplary inhibitors include, but are not limited to, t-butyl catechol, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, copper naphthenate, triphenyl antimony. When present, the filler material can be one or more organic materials, one or more inorganic materials or a combination thereof. Examples of organic fillers include, but are not limited to, low shrinkage additives, polyethylene,

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17/38 cross-linked polyesters, cross-linked acrylic, cross-linked urethane, abs, graphite, graphene, carbon nanotubes and carbon fibers. Examples of low shrinkage additives include polyvinyl acetate, polystyrene, polyethylene and the like. Examples of inorganic fillers include, but are not limited to, calcium carbonate, clay, talc, volastonite, fly ash, glass microbalions, zinc sulfate, nano clay, nano silica, nano zinc and glass fibers. When present, the coloring agent can be any standard pigment additive known to modify the color of a resin composition. Examples of coloring agents include, but are not limited to, iron oxide, carbon black and titanium oxide.

[0053] The curing of the present composition can be facilitated through the use of an organometallic compound, UV, electron beam, heat or other peroxide systems known in the art. In the preferred embodiments, where a peroxide system is used, the peroxide system can be a peroxide or hydroperoxide, preferably in concentrations of 0.5 to 4%. Examples of peroxides or hydroperoxides include, but are not limited to, benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide (MEKP), t-butyl perbenzoate and the like. When curing by heat, the present composition can cure at a temperature of 50 to 350 ° C, depending on the initiator used. When cured, the present composition may exhibit one or more characteristics that are particularly notable for the uses described herein. As a first illustrative example, when cured, the present composition may exhibit a heat deflection temperature greater than 140 ° F; alternatively, greater than 160 ° F; or, alternatively, greater than 180 ° F. As a second illustrative example, when cured, the present composition can elongate more than 5%; alternatively, greater than 6%; or, alternatively, greater than 7% determined according to the test methodology established in ASTM D638, which is incorporated in this document by reference in its entirety. As one skilled in the art would appreciate, this stretching metric is illustrative of the elasticity of the present composition. As a third illustrative example,

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18/38 when cured, the present composition may be able to withstand more than 4 pulls; alternatively, more than 10 pulls; alternatively, more than 20 tractions; alternatively, more than 50 tractions; alternatively, more than 100 tractions; or, alternatively, more than 200 tractions. One skilled in the art would appreciate that a traction metric is a standard value for determining durability. An experimental protocol for determining the number of pulls is disclosed in Example 1 of this document. In preferred embodiments, when cured, the present composition exhibits a combination of the heat deflection properties, durability and elasticity described in this document. One skilled in the art will find it surprising that the present composition exhibits a combination of these characteristics. For example, it is difficult to design a composition that is durable and elastic in the technique.

[0054] The present composition described so far can be combined with a pre-gel and / or promotion package to form an adhesive composition particularly suitable for being sprayed on an object and forming a sealant resistant to changes in temperature and pressure associated with the autoclave under vacuum.

[0055] The pre-gel may comprise styrene, a clay composition and one or more additives. The styrene of the pre-gel can comprise about 10 to about 40%; alternatively, 10 to 40%; alternatively, 15 to 35%; alternatively, 15 to 30%; alternatively, 15 to 25%; or alternatively, 20 to 25% of the total weight of the present composition. One or more additives may comprise one or more of the additives described in this document. The pre-gel clay composition comprises a composition in which the clay is present. One skilled in the art would appreciate the types of clay compositions that would be suitable for use in the applications described in this document. For example, the clay composition may comprise nano-clay, an example available from Neutrino Corporation (Tehran, Iran) under the trade name Cloisite® 10A.

[0056] As an illustrative method to make this composition, styrene and methyl methacrylate are added together and heated to approximately 80

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19/38 ° F. A clay composition is then slowly and incrementally added to the mixture and subjected to a high shear mixture. When no agglomeration or minimal agglomeration is present, the mixture is ready for further processing. The mixture is then combined with styrene and the present composition is subjected to a high shear mixture for 10 minutes. If one or more additives are being used as a chemical curing agent, such as cobalt octoate or cobalt hydroxide, the chemical curing agent can be added to the mixture and subjected to another 10 minutes of high shear mixing. Finally, and optionally, one or more additives are added to the mixture and subjected to a high shear mixture for a total of 10 minutes or per additive, depending on the additive introduced.

[0057] In the modalities in which the present composition is combined with a pre-gel and / or promotion package, the total composition may have one or more of the following characteristics: gel time of approximately 75 minutes; viscosity of 75-100 cps at 25 ° C; and / or a percentage of non-volatile material ranging from 20 to 40%; preferably 30-40%; or ideally 30-35%.

[0058] The present composition can also be combined with one or more additional resins. An illustrative example of an additional resin is an unsaturated polyester resin. The unsaturated polyester resin can be any resin that is prepared by the polyesterification of a polyol with a polycarboxylic acid, at least a portion of which contains ethylenic unsaturation. Typical useful unsaturated polyester resins contain as polyol any of the low molecular weight glycols, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, butylene glycol, neopentyl glycol and the like; and contain maleic acid, maleic anhydride or fumaric acid or possibly other unsaturated dicarboxylic acids, such as itaconic acid, citraconic acid; and may contain amounts of other dicarboxylic acids or polycarboxylic acids that do not contain ethylenic unsaturation, such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, azelaic acid and the like. Polyesters can also be modified, for example, by adding

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20/38 cyclopentadiene or dicyclopentadiene. The addition of one or more additional resins to the present composition should not affect the composition's ability to adhere to the substrates identified in this document.

[0059] The core-coated vinyl ester resin, the first part of the present composition or the present composition of any embodiment described above can be used in various methods readily apparent to those skilled in the art. For example, the grooves in a substrate can be filled using the core coating vinyl ester resin, the first part of the present composition or the present composition as an adhesive coating described in this document in several ways. The substrate can be a raw printed object or an object that has been machined to a certain extent. As a first illustrative example, the material mixed by hand (dressing and raw material in appropriate proportions, properly mixed in a glass or bucket) can be applied with a squeegee, roller, trowel, spatula, paint stick, brush or any other mechanical means that facilitates to fully print the coating material in the groove. As a second illustrative example, the spray tip can be removed from the spray apparatus without removing the static mixers. This configuration can be used to extrude the coating material initiated properly into the grooves of the object. Depending on the size, shape and number of grooves present on the substrate surface, a combination of the first and second illustrative examples can be used most effectively, representing substantially a third exemplary application method. In cases of very large or deep grooves, it may be necessary to use a vibrating energy source to ensure that the adhesive coating material fully fills the grooves on the substrate surface without the adhesive coating material containing air grooves.

[0060] In the embodiments, the vinyl ester resin of the main shell, the first part of the present composition or the present composition can be applied to the surface of a substrate as an adhesive coating in an additive manner, wherein the present composition is applied to the surface of allowed to cure

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21/38 and then another layer of the vinyl ester resin from the main shell, the first part of the present composition or the present composition is applied to the cured layer of the adhesive coating. This method can be repeated until the desired surface is achieved. This application method is particularly preferred when large grooves are present on the substrate surface. In these embodiments, it is preferable to allow the cured material to reach a temperature within approximately 10 ° F of the initial temperature of the substrate surface before another layer of the present composition is applied. The application and subsequent curing of the adhesive coating, when applied to the surface of a substrate, can result in an exothermic reaction. Therefore, a cooling period is necessary to obtain ideal physical characteristics of the adhesive coating. Each layer of the adhesive coating can be applied where the average thickness per layer ranges from 0.025 to 0.25 inches; or, alternatively, 0.08 to 0.12 inches. Once the coating is completely cured, the object can be smoothed and / or shaped as needed, according to standard processing techniques (eliminating sharp edges, etc.).

[0061] The average thickness of the adhesive coating on the substrate surface can vary from 0.05 to 0.50 inches; alternatively, 0.1 to 0.45 inches; alternatively, 0.15 to 0.40 inches; alternatively, 0.20 to 0.40 inches; alternatively, 0.20 to 0.35 inches; alternatively, 0.20 to 0.30 inches; or alternatively; about 0.25 inches; or, alternatively, 0.25 inches to achieve the performance noted in this document.

[0062] In preferred embodiments, the cured adhesive coating is applied to the surface of a substrate (or another layer of adhesive coating as appropriate), where the cured adhesive coating shows no evidence or minimal evidence of thermal dimensional changes. One skilled in the art would readily appreciate what no evidence or minimal evidence of thermal dimensional changes represents. For example, no evidence or minimal evidence of thermal dimensional changes means that the eye

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22/38 human cannot identify peaks or valleys present in the cured adhesive coating. As another example, no evidence or minimal evidence of thermal dimensional changes represents a finished surface profile less than 0.10 mm, less than 0.05 mm; alternatively, less than 0.04 mm; or, alternatively, less than 0.03 mm.

[0063] Although the adhesive composition exhibits self-leveling properties, which in turn avoids the need for significant post-curing processing, the adhesive coating can be finished using conventional means of painting, sanding and / or polishing. When finished, the surface of the object has no evidence or minimal evidence of thermal dimensional changes, as defined in this document.

[0064] In application methods in which the present composition is being used as a sealant, particularly in combination with a pregel and / or promotion package, the present composition can be sprayed onto the substrate in a single or a series of applications to obtain a layer in the range of 0.004 to 0.01 inches, preferably 0.006 to 0.008 inches. After each application, the coating is cured for one hour at room temperature and then post-cured at 120 ° C for another hour. When the present composition is being used as a sealant, the present composition is particularly suited to withstand thermal cycling.

[0065] The present composition can be used in a method of manufacturing a mold or prototype comprising (a) forming a substrate comprising a polymer body having a surface; (b) applying an adhesive coating to the surface of the polymer body, wherein the adhesive coating comprises a core-coated vinyl ester resin; and (c) curing the adhesive coating. The method may further comprise (d) cooling the cured adhesive coating to 10 ° F from the initial substrate temperature;

(e) applying the adhesive coating; and (f) curing the adhesive coating applied in step (e). Steps (d) to (e) can be repeated as needed until the desired thickness of the adhesive coating or sealant is achieved. In

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23/38 preferred modes, each application of the adhesive to the substrate results in an average thickness of the adhesive coating greater than 0.08 inches. The adhesive coating may further comprise urethane acrylate. The adhesive coating can also comprise any embodiment of the present composition described in this document. After the adhesive coating is applied and subsequently cured, the surface profile of the adhesive coating is less than the original surface profile of the substrate surface. In the modalities, the formation step (a) is an additive manufacturing method, preferably large-scale additive manufacturing methods.

[0066] The method of manufacturing a mold or prototype can also include the application of paint or other sealant to the adhesive coating.

[0067] Now returning to the figure in which a modality of the present composition is applied to a substrate in the manner described in this document to form an object, particularly an article of manufacture. Although the figure discloses a modality of the present composition applied to a substrate to form an object, one skilled in the art would appreciate that the teachings of the present disclosure would not be limited to these modalities.

[0068] FIG. 1 shows a schematic diagram, in cross section, of a polymer substrate 1, the surface of which was covered by the present composition to form an adhesive coating 2. Coating 2 further contains particles of core coating 3. Substrate 1 has a surface as manufactured 4 with a characteristic surface profile 5. Since the coating 2 has a degree of self-leveling, the outer surface 6 of the coating has a surface profile 7 that is substantially smaller than the surface profile 5 of the substrate 1, as described in more details in this document. It will be appreciated that coating 2 can be applied in more than one coat and it will be even more appreciated that, in general, the surface profile of subsequent coatings will be progressively smaller (ie the surface becomes smoother as more coats are applied. applied).

[0069] Although specific modalities have been described in detail,

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24/38 It will be appreciated by those skilled in the art that various modifications and alternatives to these details can be developed in the light of the general teachings of disclosure. In particular, the present composition described in this document can be used in several different ways and in different applications, not necessarily involving objects made by additive manufacturing. Therefore, the disclosure presented here is intended to be illustrative only and not to limit its scope and should receive the full extent of the attached claims and any equivalents thereof.

EXAMPLES

Ί0070ΊExample 1. Durability. The durability of the present composition was tested by evaluating the number of stresses that an adhesive coating was able to withstand before the coating failed. The results of this analysis are shown in Table 3. Comparator A is a product commercially available from Valvoline (Lexington, KY) sold under the trade name Repair Plastic 3 PiloGrip®. Comparator B is a product commercially available from Valvoline (Lexington, KY) sold under the trade name PlioGrip® Finishing Cream. Comparator C is a product commercially available from Valvoline (Lexington, KY), sold under the trade name Panel 60 PlioGrip®. Comparator D is a product commercially available from Clausen (Fords, NJ) sold under the trade name Z-Glas Comparator E is a product commercially available from 3M (St. Paul, MN) sold under the trade name Flexible parts repair adhesive EZ sand. Comparator F is a product commercially available from 3M (St. Paul, MN) sold under the brand name Dent Filling Compound Body Filler. In this test, each adhesive coating was applied to the ABS filled with carbon fiber and the failure of its adhesive or cohesive properties was evaluated.

Table 3.

Comp. THE Comp. B Comp. Ç Comp. D Comp. AND Comp. F Composition Current No. 4 4 1 4 4 3 > 60

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25/38

Pulls

[0071] The previous results show that the present composition is significantly more durable than commercially available substitutes.

[0072] Example 2. Accession. The adhesion of the present composition has been tested according to the ASTM D4541 standard, which is incorporated in this document by reference in its entirety. In short, the adhesive composition is applied to the back of a cart, which is then placed on a substrate for testing. After the appropriate curing conditions, as set out in the data sheet for each product, a band saw or cutter was used to cut around the cart through the coating for or just the substrate. Then, manual pressure was exercised through the use of a PosiTest adhesion tester, commercially available from DeFelsko (Ogdensburg, NY). The pressure that resulted in the failure of the adhesive composition is shown in Table 4. The silicone adhesive used in this example is commercially available from Devco (Tulsa, OK), sold under the trade name S120. Modality A and Modality B observed in Table 4 differ only in viscosity due to the use of a different monomer in the composition.

Table 4.

Sticker of Silicone Core Coated Vinyl Ester Resin Only Current Composition Modality A Current Composition Mode B psi 277 229 1313 1104

[0073] The previous results show that both modalities of the present composition adhere to the substrate significantly better than the commercially available silicone adhesive. In addition, the previous results show that the present composition adheres to the substrate significantly better than a composition containing only a core-coated vinyl ester resin. From these results, it is shown that

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26/38 the components act in a synergistic and surprising effect to achieve the reported adhesion properties.

[0074] Example 3. Elasticity. The elasticity of the present composition has been tested according to the ASTM D638 standard, which is incorporated in this document by reference in its entirety. In summary, the cured adhesive composition is placed between a fixed member and a movable member secured by claws. The movable member is then removed from the fixed member in a controlled manner, exerting an elastic tension on the present composition. The test measured the maximum elongation, shown in Table 5.

Table 5:

Vinyl Ester Resin Only Core Coating Current Composition 5% Greater than or equal to 8%

[0075] The previous results show that the present composition is more elastic than an aspect of the present composition. One skilled in the art would readily appreciate that the present composition is surprisingly elastic, given the other physical properties described in this document, particularly the adhesion and durability properties described in Examples 1 and 2. MODALITIES

[0076] The previous description describes, illustrates and exemplifies one or more particular modalities of an adhesive composition. This description is not provided to limit disclosure to the modalities described in this document, but to explain and teach various principles to enable a person skilled in the art to understand those principles and, with that understanding, be able to apply them to practice not only the modalities described in this document, but also other modalities that may come to mind according to these principles. The scope of this disclosure is intended to cover all such modalities that may be within the scope of the attached claims, literally or under the doctrine of equivalents. This disclosure notes that several modalities are disclosed in this document, at least including:

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A. A composition comprising a core-coated vinyl ester and urethane acrylate.

TO 1. The composition of A, wherein the core coating vinyl ester comprises a vinyl ester resin and one or more core coating polymers.

A.2. The composition of any prior embodiment, wherein the core-coated vinyl ester resin comprises 25 to 95%; preferably 50 to 95%; more preferably, 60 to 95%; or optimally 75 to 95% of the total weight of the current composition.

A.3. The composition of any previous embodiment, wherein the urethane acrylate comprises 2 to 25%; preferably 5 to 20% of the total weight of the present composition.

A.4. The composition of any previous embodiment, further comprising a monomer.

A.4.a. The composition of A.4, wherein the monomer comprises 0.1 to 40%; preferably 0.1 to 30%; and more preferably 0.1 to 20% of the total weight of the present composition.

A. 5. The composition of any previous modality, further comprising one or more additives.

A. 5.a. The composition of A.5., Wherein the one or more additives comprise 0.1 to 40%; preferably 0.1 to 20%; and most preferably 0.1 to 15% of the total weight of the present composition.

B. A composition comprising a first part comprising a core-coated vinyl ester and a second part comprising a urethane acrylate.

B. 1. The composition of B, where the first part comprises 25 to 95%; preferably 30 to 95%; more preferably, 50 to 90%; and ideally, 65 to 75% of the total weight of the present composition.

B.1.a. The composition of B or B.1., Wherein the core-coated vinyl ester comprises 60 to 95%; preferably 65 to 95%; more

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Preferably 28/38, 70 to 95%; and ideally, 75 to 95% of the total weight of the first part.

B1 .b. The composition of B or B.1 .a., Wherein the first part further comprises a monomer and / or one or more additives.

B.l.b.i. The composition of B.1.b., wherein the monomer comprises 10 to 80%; preferably 10 to 70%; and most preferably, 20 to 40%; and ideally, 25 to 35% of the total weight of the first part.

B.2. The composition of B or B.1., Wherein the second part comprises 2 to 25%; preferably 5 to 20%; more preferably, 5 to 15%; and ideally, 10 to 15% of the total weight of the present composition.

B.2.a. The composition of B.2, wherein the urethane acrylate comprises 40 to 90%; preferably 50 to 90%; more preferably, 60 to 90%; and ideally, 70 to 90% of the total weight of the present composition.

B.2.b. The composition of B.2 or B.2.a., wherein the second part further comprises a monomer and / or one or more additives.

B.2.b.i. The composition of B.2.b., wherein the one or more additives facilitate the curing of the composition and / or the cross-linking of the components of the composition.

B.3. The composition of any embodiment B-B.2.b.i., Further comprising a third part comprising a monomer.

B.3.a. The composition of B.3., In which the third part comprises 1 to 75%; preferably 2 to 40%; more preferably, 2 to 40%; and even more preferably, 10 to 30%; and ideally, 10 to 20% of the total weight of the present composition.

The composition of any prior embodiment, wherein the core-coated vinyl ester comprises 45 to 95%, 50 to 95%, 50 to 90%, 55 to 85%, 60 to 80%, 65 to 75% or 70 to 75 % of the total weight of the composition.

B.4. The composition of any previous embodiment, in which urethane acrylate comprises 5 to 25%, 5 to 20%, 5 to 15% or 10 to 15% by weight

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29/38 total of the composition.

B.5. The composition of any previous embodiment, wherein the urethane acrylate comprises 40 to 80%, 50 to 70% or 60 to 70% of the total weight of the second part.

B.6. The composition of any previous embodiment, wherein the second part comprises 2 to 25%, 5 to 20%, 5 to 15% or 10 to 15% of the total weight of the composition.

C.1. The composition of any previous modality, in which the vinyl ester resin is produced from the bisphenol-A diglycidyl ether (DGEBA) and methacrylic acid.

C.2. The composition of any previous modality, in which the vinyl ester resin is produced from a reaction between glycidyl methacrylate and a multifunctional phenol.

C.3. The composition of any previous modality, in which the core coating polymers are selected from polymerized versions of: butadiene; butadiene and styrene; butadiene, methyl methacrylate and styrene; butadiene, alkyl methacrylate and alkyl acrylate; butadiene, styrene, alkyl acrylate, alkyl methacrylate and methacrylic acid; butadiene, styrene, alkyl acrylate, alkyl methacrylate, methacrylic acid and low molecular weight polyethylene (as a flow modifier); butyl acrylate and methyl methacrylate; alkyl methacrylate, butadiene and styrene; alkyl acrylate, alkyl methacrylate and glycidyl methacrylate; and alkylacrylate and alkylmethacrylate, preferably butadiene.

C. 4. The composition of any previous embodiment, wherein the core coating polymer has an average diameter of 50 to 350 nm, preferably 100 to 300 nm, more preferably 150 to 250 nm; and ideally 200 nm.

D. 1. The composition of any previous embodiment, wherein urethane acrylate is a reaction product of a diisocyanate, an OH functional molecule with an olefinic double bond and an optional material containing mono-,

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30/38 di- or multifunctional.

D.1.a. The composition of D. 1., in which the diisocyanate is aromatic or aliphatic.

D.l.a.i. The composition of D.1. or D.1.a., where the diisocyanate is selected from diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) or a combination of them.

D.2. The composition of any previous embodiment, in which the urethane acrylate has an average hydroxy content of 100 to 115.

D.3. The composition of any prior embodiment, wherein the urethane acrylate has a carbamate bond content of 0.1 to 10%; preferably 0.5 to 5%; more preferably, 0.5 to 4%; and ideally 0.5 to 3%.

D.4. The composition of any previous embodiment, wherein the urethane acrylate has a molecular weight of 600 to 5000, preferably 1500 to 3000.

D.5. The composition of any previous embodiment, in which the urethane acrylate has a viscosity of 4000 cps at 60 ° C.

D.6. The composition of any previous modality, in which urethane acrylate comprises two or more attributes of modalities D.2. through D.5.

D. 7. The composition of any previous modality, in which urethane acrylate comprises three or more attributes of the modalities D.2. through D.5.

E. 1. The composition of any previous embodiment, in which the monomer is selected from styrene, methyl methacrylate, vinyl toluene, hydroxymethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl methacrylate, ethyl hydroxy acrylate, hydroxy propyl acrylate, hydroxypropyl methacrylate, methyl alpha styrene and divinyl benzene. Other exemplary monomers include o-methyl styrene, m-methyl styrene, p-methyl styrene, methyl acrylate, t-butyl styrene, diallyl phthalate, trialyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane thmethacrylate; ethoxylated trimethylolpropane triachlate; glicehlpropoxy triacrylate; propylene glycol diachlate; ethylene glycol diachlate; ethylene glycol dimetachlate; diachlato

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31/38 ethylene glycol; tetraethylene glycol diacrylate; triethylene glycol dimethacrylate; tripropylene glycol dimethacrylate; polypropylene glycol diacrylate; polyethylene glycol dimeacrylate; butanediol diacrylate; butane-diol dimethacrylate; pentaerylitol triacrylate; pentaerythritol tetra-acrylate; ethoxylated bisphenol A diacrylate; hexane diol diacrylate; dipentaerythritol monohydroxypenta acrylate; neopentyl glycol diacrylate; neopentyl glycol dimethacrylate; and tris (2hydroxyethyl) isocyanurate triacrylate; preferably styrene.

E. 2. The composition of any prior embodiment, wherein the composition further comprises a pre-gel.

E.2.a. The composition of I.1., Wherein the pre-gel comprises 10 to 40%; preferably 15 to 35%; more preferably, 15 to 30%; and even more preferably, 15 to 25%; and ideally, 20 to 25% of the total weight of the composition.

E. 2.b. The composition of 1.1 or 1.1.a, wherein the pre-gel comprises styrene, a clay composition and one or more additives.

F. 1. The composition of any previous modality, in which one or more additives are selected from an air / wetting agent, rheology modifier, thixotropic synergist, inhibitor, initiator, catalyst, surfactant, filler and paraffin wax.

F. 1 .a. The composition of F.1., In which the inhibitor is selected from t-butyl catechol, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, copper naphthenate and triphenyl antimony; or a combination of them.

F.1 .b. The composition of F.1., In which the catalyst is selected from cobalt naphthenate, cobalt octoate, cobalt hydroxide, potassium octoate, potassium naphthanate, a manganese salt, an iron salt, N, Ndimethylaniline and N, N-dimethyl-p-toluidine; or a combination of them.

F.1 .c. The composition of F.1., In which the rheology modifier is selected from pyrogenic silica, clay, organo-treated clay, castor oil and a polyamide; or a combination of them.

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F.1 .d. The composition of F.1 in which the air release agent / wetting agent is selected from polyacchlate, silicone and mineral oil; or a combination of them.

F.1 .e. The composition of F.1., In which the coloring agent is selected from iron oxide, carbon black and titanium oxide; or a combination of them.

F. 1 .g. The composition of F.1., Wherein the filling material comprises an organic or inorganic filling material.

F.1 .g.i. The composition of F.1 .g, in which the organic filler material is selected from polyethylene, a cross-linked polyester, a cross-linked acrylic, a cross-linked urethane, abs, graphite and carbon fibers; or a combination of them.

F. 1 .g.ii. The composition of F.1 .g., In which the inorganic filler material is selected from calcium carbonate, clay, talc, volastonite, fly ash, glass microbalions, zinc sulfate, nano clay, nano silica, nano zinc and glass fibers; or a combination of them.

G.1. The composition of any prior embodiment, wherein the composition further comprises one or more additional resins.

G. 1.a. The composition of G.1, wherein the one or more additional resins are one or more unsaturated polyester resins.

G. 1 .a.i. The composition of G.1 .a., In which the unsaturated polyester resin is prepared by the polyesterification of a polyol with a polycarboxylic acid.

G.l.a.ii. The composition of G.1.a. or G.1.ai, wherein the unsaturated polyester resin comprises ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, butylene glycol or neopentyl glycol.

G.1 .a.iii. The composition of any modality G.1 .a. to G.1 .a.ii, in which the unsaturated polyester resin is selected from maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid,

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33/38 phthalic, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid and azelaic acid.

G.l.a.iv. The composition of any modality G.1 .a. to G.l.a.iii, in which at least a portion of the unsaturated polyester resin contains ethylenic unsaturation.

G.1 .a.v. The composition of any modality G.1 .a. to G.l.a.iv, in which the unsaturated polyester resin was modified by cyclopentadiene or dicyclopentadiene.

H.1. The composition of any previous embodiment, wherein when the composition is cured, the composition exhibits a heat deflection temperature greater than 140 ° F, preferably greater than 160 ° F; and more preferably, greater than 180 ° F.

H.2. The composition of any previous embodiment, wherein the composition can elongate more than 5%, preferably more than 6%; more preferably, more than 8%.

H.2.a. The composition of H.2., In which the elongation is determined according to the ASTM D638 standard.

H.3. The composition of any previous embodiment, in which the present composition may be able to withstand more than 4 pulls; preferably, more than 10 pulls; more preferably, greater than 20 tractions; even more preferably, greater than 50 pulls; even more preferably, more than 100 pulls; and, ideally, more than 200 tractions.

H. 4. The composition of any previous modality, in which the composition is cured using an organometallic compound, UV, electron beam, heat or other peroxide systems.

I. An object comprising a polymer body having a surface; and an adhesive coating on the surface of the polymer body, wherein the adhesive coating comprises core-coated vinyl ester resin.

11. The object of I, wherein the adhesive coating further comprises a urethane acrylate.

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12. The object of I or 11, in which the core-coated vinyl ester resin, the first part of any previous embodiment, or the composition of any previous embodiment, has an average thickness greater than 0.08 inches.

13. The object of any modality I to I2, in which the adhesive coating has an average thickness per layer of 0.025 to 0.25 inches, preferably 0.08 to 0.12 inches.

I4. The object of any of modalities I to I3, in which the average thickness of the adhesive coating on the substrate surface is 0.05 to 0.50 inches; preferably 0.1 to 0.45 inches; more preferably, 0.15 to 0.40 inches; even more preferably, 0.20 to 0.40 inches; even more preferably, 0.20 to 0.35 inches; and ideally, 0.20 to 0.30 inches.

15. The object of any of the modalities I to I4, in which the object is impermeable or substantially impermeable to gas or liquid when the adhesive coating is applied to the surface of the polymer body and allowed to cure.

16. The object of any of the modalities I to I5, in which the adhesive coating inhibits the entry of gas or liquid into the substrate.

17. The object of any of the modalities I to I6, in which the adhesive coating fills empty spaces, geometric imperfections, missing or broken granules, underfilled cavities or contours or surface textures of the substrate.

18. The object of any modality I to I7, in which the adhesive coating further comprises one or more crosslinking agents, curing agents, thixotropic agents, air / wetting agents, coloring agents, inorganic filling agents, organic fillers, lightweight fillers, surfactants, inorganic nanoparticles, organic nanoparticles and combinations thereof.

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19. The object of any of modalities I to 18, in which the substrate comprises acrylonitrile-butadiene-styrene, polyphenylene sulfide, polypenyl sulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid or combinations thereof.

110. The object of any modality I to I9, in which the substrate is reinforced with glass fibers, carbon fibers, bamboo or combinations thereof.

111. The object of any of the modalities I to 110, in which the adhesive composition adheres to the surface of the polymer body and forms a bond between the adhesive coating and the substrate, where the bond strength between the coating and the substrate is greater than 300 psi.

112. The object of any embodiment I to 111, in which the surface of the polymer body has a first surface profile and the surface of the coating after curing has a second surface profile smaller than the first surface profile.

113. The object of any modality I to 112, in which the substrate has a surface profile of 1.0 to 10 mm; preferably 2 to 7.5 mm and more preferably 2.5 to 5.0 mm before adding the composition.

114. The object of any modality I to 113, in which the adhesive coating, when cured on the surface of the polymer body, has a finished surface profile of less than 0.1 mm; preferably less than 0.08 mm; more preferably, less than 0.05 mm; even more preferably, less than 0.04 mm; and ideally, less than 0.03 mm.

115. The object of any of modalities I to 114, where the object is a composite polymer article.

116. The object of any of modalities I to 115, in which the object or article composed of polymer is generated by means of an additive manufacturing method.

117. The object of any of modalities I to 116, in which the object or article composed of polymer is produced using the method of

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36/38 large-scale additive manufacturing.

118. The object of any modality I to 117, wherein the adhesive coating comprises a composition of any modality A to H4.

J. A method for making an object, comprising:

(a) forming a substrate comprising a polymer body having a surface;

(b) applying an adhesive coating to the surface of the polymer body, wherein the adhesive coating comprises core-coated vinyl ester resin;

(c) cure the adhesive coating applied in (b).

J1. The J method, wherein the adhesive coating further comprises urethane acrylate.

J2. The J or J1 method, in which the application step comprises applying the composition with a squeegee, roller, trowel, spatula, paint stick, brush or other mechanical means.

J3. The method of any modality J to J2, wherein the application step comprises spraying the adhesive coating on the surface of the polymer body.

J3.a. The method of J3, wherein the adhesive coating forms a layer with a thickness of 0.004 to 0.01 inches, preferably 0.006 to 0.005 inches.

J3.b. The J3.a. J3 method, wherein the adhesive composition further comprises a pre-gel and / or promotion package, as defined by any modality from E2 to E2.b.

J4. The method of any of the modalities J to J3.b, wherein the adhesive coating is applied and allowed to cure and then another layer of the adhesive coating is applied to the cured layer.

J5. The method of any modality J to J4, in which the application stage comprises the application of the composition to reach a layer of the

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37/38 composition with a thickness greater than 0.08 inches.

J6. The method of any modality J to J5, in which the cure is performed using UV light, an electron beam, an organometallic compound, a peroxide or heat.

J7. The method of any modality J to J6, in which the curing is carried out by heating the substrate to a temperature of 50 to 350 ° C.

J8. The method of any modality J to J7, in which when the adhesive coating is cured, the adhesive coating exhibits a heat deflection temperature greater than 140 ° F; preferably greater than 160 ° F; and more preferably, greater than 180 ° F.

J9. The method of any of the modalities J to J8, in which the method further comprises:

(d) cooling the cured adhesive coating to 10 ° F from the initial temperature of the substrate surface;

(e) applying an additional layer of the adhesive coating; and (f) curing at least one layer of adhesive coating applied in step (e) and, optionally (g) repeating steps (d) to (f) until the desired average thickness of the adhesive coating is achieved.

J10. The method of any of the modalities J to J9, in which the object is a composite polymer article.

J11. The method of any modality J to J10, in which the polymer composite object or article is generated by means of an additive manufacturing method.

J12. The object of any of the modalities J to J11, in which the polymer composite object or article is produced using the method of manufacturing additives on a large scale.

J13. The method of any modality J to J12, in which the polymer composite object or article is a mold or prototype.

J14. The method of any modality J to J13, in which the

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The adhesive coating comprises a composition of any type A to

H4.

Claims (21)

1. Composition, characterized by comprising a vinyl ester with a core coating and an urethane acrylate. 2. Composition according to claim 1, characterized in that the core-coated vinyl ester resin comprises 25 to 95% of the total weight of the composition. Composition according to claim 1 or 2, characterized in that the core-coated vinyl ester resin comprises core-coated polymer with an average diameter ranging from 50 to 350 nm. 4. Composition, according to any previous claim, characterized by the fact that urethane acrylate comprises 2 to 25% of the total weight of the composition. Composition according to any preceding claim, characterized in that it further comprises a monomer. Composition according to any preceding claim, characterized in that it also comprises one or more unsaturated polyester resins. 7. Composition, according to any previous claim, characterized by the fact that the composition has a carbamate bond content of 0.1 to 10%. 8. Composition according to any preceding claim, characterized in that it further comprises one or more additives. 9. Composition according to claim 8, characterized in that one or more additives comprise a crosslinking agent, curing agent, thixotropic agent, air / wetting agent, coloring agent, air release, inorganic filler or organic, light charge, surfactant, inorganic or organic nanoparticles or their combinations. 10. Composition according to any one of the preceding claims, characterized by the fact that when the composition is cured, the composition exhibits a heat deflection temperature greater than 140 ° F and / or the composition can elongate more than 5%. Petition 870190100686, of 10/08/2019, p. 59/100 2/3 11. Polymer composite article, characterized by the fact that it comprises: a substrate comprising a polymer body having a surface; and, an adhesive coating on the surface of the polymer body, wherein the adhesive coating comprises core-coated vinyl ester resin. 12. Composite article according to claim 11, characterized in that the adhesive coating further comprises a urethane acrylate and, optionally, one or more additives. 13. Composite article according to claim 11 or 12, characterized in that the adhesive coating, when cured, has an average thickness greater than 0.08 inches. 14. Composite article according to any one of claims 11 or 13, characterized by the fact that the substrate comprises acrylonitrile butadiene styrene, polyphenylene sulfide, polyphenyl sulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid or combinations thereof, each of which can be optionally reinforced with glass fibers, carbon fibers, bamboo or combinations thereof. 15. Composite article according to any one of claims 11 to 14, characterized by the fact that the bond strength between the substrate surface and the adhesive coating after curing the adhesive coating is at least 300 psi. 16. Composite article according to any one of claims 11 to 15, characterized by the fact that the adhesive coating after the adhesive coating is cured has a finished surface profile of less than 0.10 mm. 17. Method for manufacturing a composite polymer article, characterized by the fact that it comprises: (a) forming a substrate comprising a polymer body having a surface; (b) applying an adhesive coating to the surface of the polymer body, Petition 870190100686, of 10/08/2019, p. 60/100 3/3 wherein the adhesive coating comprises core coating vinyl ester resin; (c) cure the adhesive coating. 18. Method according to claim 17, characterized in that the adhesive coating further comprises a urethane acrylate and, optionally, one or more additives. 19. Method according to claim 17 or 18, characterized in that the substrate comprises acrylonitrile butadiene styrene, polyphenylene sulfide, polypenyl sulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid or combinations of each of which it can be optionally reinforced with glass fibers, carbon fibers, bamboo or combinations thereof. 20. Method according to any one of claims 17 to 19, characterized in that the application step comprises applying the adhesive coating to reach a layer of the composition with a thickness greater than 0.08 inches. 21. Method according to any one of claims 17 to 20, characterized in that it further comprises: (d) cooling the cured adhesive coating to 10 ° F from the initial temperature of the substrate surface; (e) applying an additional layer of the adhesive coating; (f) curing the adhesive coating applied in step (e); and optionally, (g) repeat steps (d) - (f) until the desired average thickness of the adhesive coating is achieved.