BR112019021114B1 - ADHESIVE COMPOSITIONS AND METHODS FOR COATING OBJECTS - Google Patents

Abstract

An adhesive composition comprising a core coating vinyl ester and a 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

JOINT RESEARCH AGREEMENT

[0001] Aspects of the present invention have been 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 aspects of the present invention were made and aspects of the present invention were made as a result of activities carried out within 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.

FUNDAMENTALS 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 to manufacture objects. However, objects made through additive manufacturing have a rough surface and are consequently 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 for improving 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, grinding the object is time consuming, creates a large amount of dust that is often problematic due to its carbon or other fiber content, and limits the usefulness of the additive manufacturing process for real-world applications. Additionally, paint failures are common due to the paint's inability to withstand object expansion and contraction.

[0005] Existing coating compositions for objects made through 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. Furthermore, 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 render 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, but are not limited to, paint or adhesive sealant clumping together and cracking. Therefore, there is a need for a coating composition that can overcome the known problems associated with large objects made by additive manufacturing.

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

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

SUMMARY

[0009] The present disclosure relates to a composition comprising a core coating vinyl ester resin and a urethane acrylate. The core shell vinyl ester resin may comprise 25 to 95% of the total weight of the composition and/or contain core shell polymer having an average diameter of 50 to 350 nm. The 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 may have a carbamate binding content of 0.1 to 10%; exhibits a heat deflection temperature greater than 140° F; and/or the composition may elongate 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 coating vinyl ester resin or the actual ester resin composition core coating vinyl and urethane acrylate. The polymer composite article is made from a substrate where the type of substrate can be acrylonitrile-butadiene-styrene, polyphenylene sulfide, polypenylsulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid or combinations thereof. These types of substrates 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 may be applied in such a way that the composition has an average thickness greater than 0.08 inches on the surface of the substrate. Once cured, the adhesive coating (1) adheres to the surface of the substrate; (2) the bond strength between the adhesive coating and the surface of the substrate is greater than 300 psi; and/or (3) the adhesive coating, once cured, 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 coating 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 by using a sprayer to spray the composition onto the object. The result of the application step can be an adhesive coating layer greater than 0.08 inch thick to achieve the desired properties.

[0015] In some cases, multiple applications of the adhesive coating are warranted. In these cases, the pre-applicated adhesive coating must cool to within 10°F of the initial surface temperature of the substrate. Then an additional application of the adhesive coat can be done over the previous application of the adhesive coat and allowed to cure.

BRIEF DESCRIPTION OF THE DESIGN

[0016] The present disclosure can be better understood from the detailed description below, when read with the attached drawing. Features 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.

DETAILED DESCRIPTION

[0018] The present adhesive composition can be used as an adhesive composition that functions to fill voids of objects with a rough or uneven surface present on certain substrates. The present adhesive composition can further be used as a sealant capable of withstanding temperature and pressure changes 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 more preferably a polymer composite article made using additive manufacturing, and ideally a polymer composite article made using additive manufacturing. large-scale additive manufacturing. In preferred embodiments, the object may 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), polyphenylsulfone (PPSU), polyethersulfone (PES), polyethylene terephthalate, polybutylene terephthalate, polylactic acid (PLA ) and the like. These substrates may 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 embodiments, the present composition adheres to substrates having 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 as an adhesive coating or sealant 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 substrate of the object.

[0022] The present composition, when used as an adhesive coating or sealant, has been shown to withstand experimental and standard thermal cycling without showing underlying defects on the surface of the substrate or losing vacuum seal. Without being bound 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 embodiments, the present composition, when used as an adhesive coating or sealant, also functions to fill all common print defects on objects made by means of additive manufacturing. A non-limiting list of common defects includes pitting, geometric imperfections, missing or broken granules, underfill cavities, and surface contour/texture/resolution issues. As a result of this function, the use of the present composition results in objects with a smooth surface receptive to final finishing (eg painting). These objects are ideal for use as templates 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-coated polymer, wherein a core-coated 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 salt or triphenylphosphine is used to catalyze the reaction at a temperature of about 120°C for 4 to 5 hours. 90 to 95% of the methacrylic acid reacts to form the vinyl ester. Styrene can be added to reduce viscosity during synthesis. Alternatively, glycidyl methacrylate can be reacted with a multifunctional phenol to form a vinyl ester resin.

[0025] The core coating polymers, which are dispersed in vinyl ester resins, according to the present disclosure, are generally produced by controlled emulsion polymerization, during which the composition of the monomer feed is changed, in order to achieve a desired compositional variation on the structure of the core coating polymer. 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 ambient conditions, being produced by the polymerization of monomers such as butadiene and alkyl acrylates. . It will be understood that "rubberized under ambient conditions" means that the core of the core cladding polymer has a lower Tg at ambient temperature. Preferred core coating polymers include, but are not limited to, polymerized versions of: butadiene; butadiene and styrene; butadiene, methyl styrene methacrylate; 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, butadiene, and styrene methacrylate; alkyl acrylate, alkyl methacrylate and glycidyl methacrylate; and alkylacrylate and alkylmethacrylate. The core cladding polymer may 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 cladding polymer can be nanoparticles of amine-terminated butadiene nitrile rubber (ATBN). A suitable core cladding polymer is polybutadiene core coated with poly(co-styrene methyl methyl methacrylate). The core coating polymer can optionally be disposed within a carrier resin. The carrier resin may be a general purpose bisphenol epoxy resin or derivatives thereof known to those skilled in the art. For example, a preferred carrier resin is a diglycidyl ether of bisphenol A 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 herein, "urethane acrylate" means a reaction product of diisocyanate, an -OH functional molecule with an 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 herein, "diisocyanates" means any type of aromatic, aliphatic, alicyclic and aliphatic-aromatic 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 "-OH functional molecule with an olefinic double bond" may include partial esters of polyhydric alcohols with acrylic acid or methacrylic acid, such as, for example, ethylene glycol monoacrylate or monomethylacrylate, 1,2- or 1-, 3-propanediol, 1,4-butanediol monoacrylate or monomethacrylate, 1,6-hexanediol monoacrylate or monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane diacrylate, glycerol diacrylate, pentaerythritol triacrylate and mono(N-methylacrylamide)-ethers and mono -(N-methylolacrylamide)-ethers of ethylene glycol, propylene glycol, butanediol, hexanediol and neopentyl glycol. The “mono-, di- or multifunctional OH-containing material” may include polyfunctional alcohols, such as diols of 2 to 8 carbon atoms, for example, ethylene glycol, propanediols, butanediols, pentandiols, hexanediols, triols, such as, for example, glycerol, trimethylolpropane and hexanethiols, 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 may include the reaction product of the polycondensation 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 , 1,3-butanediol, ethylene glycol, diethylene glycol, propylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,6-hexane glycol and neopentyl glycol.

[0028] In the embodiments, the urethane acrylate has one or more of the following attributes: a carbamate binding 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 embodiments, the 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 may 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 may comprise 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 may further comprise a monomer. Exemplary monomers include, but are not limited to, styrene, methyl methacrylate, vinyl toluene, hydroxymethylmethacrylate, hydroxymethyl acrylate, hydroxyethyl 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, triallyl 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; pentaerythlitol triacrylate; pentaerythritol tetraacrylate; ethoxylated bisphenol A diacrylate; hexane diol diacrylate; dipentaerythritol monohydroxypentaacrylate; 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 may 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 core coating vinyl ester resin; 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 may 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 may comprise about 2 to about 25%; alternatively, 2 to 25%; alternatively, 5 to 20%; alternatively, 5 to 15%; or alternatively, 10 to 15% of the total weight of the present composition.

[0037] The third part may 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 coating vinyl ester resin described herein. The first part may comprise a reaction product of an epoxy resin and a methacrylic acid or derivative thereof, wherein core coating polymers are applied onto the epoxy resin. The epoxy resin may comprise a liquid epoxy resin derived from bisphenol A/epichlorohydrin. For example, a suitable bisphenol A/epichlorohydrin derivative liquid epoxy resin is D.E.R.™ 331 available from Dow (Midland, MI 48674). Another suitable bisphenol A/epichlorohydrin derivative liquid epoxy resin is EPON™ 828 resin available from Hexion Specialty Chemicals (Columbus, OH 43215). In embodiments, the bisphenol A/epichlorohydrin derivative liquid epoxy resin is a resin with an epoxide equivalent weight (g/eq) ranging from 185-192, a viscosity at 25°C of 110 to 150P, a density at 25°C of 9.7 lbs/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 embodiments, the bisphenol A/epichlorohydrin derivative liquid epoxy resin is a resin with an epoxide equivalent weight (g/eq) ranging from 182-192, an epoxide percentage ranging from 22.4 to 23.6%, an of 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 bisphenol A/epichlorohydrin derivative liquid epoxy resin described herein.

[0039] The epoxy resin may 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.

[0040] The core coating vinyl ester resin resulting from the first part may 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 embodiments, the first part may further comprise a monomer described herein, which may 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 further comprise one or more additives. Particularly suitable additives are stabilizers that facilitate the shelf life or stability of the first part and/or finally the total current composition. A suitable additive for the first part is hydroquinone available from Sigma-Aldrich 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 4-methoxyphenol 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 Sigma-Aldrich 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-hydroxyethylmethacrylate available from Sigma-Aldrich Co., LLC (St. Louis, MO 63103). When present, 2-hydroxyethylmethacrylate comprises about 1 to about 10%; 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] The urethane acrylate may 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 further comprise one or more additives. A suitable additive for the second part is methylhydroquinone. When present, the 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 may 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:

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

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

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

[0049] The core coating vinyl ester resin or the first part can be made according to the following procedure. Into a clean dry glass reactor equipped with stirrer, dry air sparge and heating mantle, 10 charge the epoxy bisphenol A epoxy and 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 maintaining the temperature between 115 and 120 °C until the epoxy number is stable. 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 herein can be added to the cooled mix to form the first part.

[0050] The urethane acrylate or the second part can be made according to the following procedure. In a clean, moisture-free glass reactor equipped with a sparge and dry air stirrer, add toluene diisocyanate and triphenylantimony to the reactor to initiate stirring. Then start the dry air sparge and add hydroxyethyl acrylate over a period of two hours, keeping the temperature below 130°F. The mixture is then held 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 cooled mixture to form the second part.

[0051] The present composition can be manufactured using a high shear mixer (e.g. a screw 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 blended to achieve the desired physical properties. In preferred embodiments, the first part and second part are added and mixed for approximately three minutes through a high shear mixer at 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 additives can be added until the present composition exhibits one or more of the following characteristics: viscosity 10,000 to 30,000 cPs at 20 rpm; viscosity from 16,000 to 20,000 cPs at 20rpm; thixotropic index greater than 3; thixotropic index greater than 4; gel time 6 to 10 minutes at room temperature; a density ranging from 0.50 to 1.0 g/cm3; or a density ranging from 0.70 to 0.80 g/cm 3 . Additives particularly suited to achieving these characteristics include an air release/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 plus fillers, paraffin wax.

[0052] When present, the air release/wetting agent is selected from polyacrylate, 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 naphanate, manganese salts, iron salts, NN-dimethyl aniline, NN-dimethyl-p-toluidine . In preferred embodiments, the present composition uses a combination of two catalysts, otherwise described herein as 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 quencher can be a chemical capable of extending the gel time and/or extending the shelf 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, crosslinked polyesters, crosslinked acrylic, crosslinked 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 filler materials include, but are not limited to, calcium carbonate, clay, talc, wollastonite, fly ash, glass microballoons, 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 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, lauroyl 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 can exhibit one or more characteristics that are particularly notable for the uses described herein. As a first illustrative example, when cured, the present composition can exhibit a heat deflection temperature in excess of 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 by more than 5%; alternatively, greater than 6%; or, alternatively, greater than 7% determined in accordance with the test methodology set forth in ASTM D638, which is incorporated herein by reference in its entirety. As one skilled in the art would appreciate, this elongation metric is illustrative of the elasticity of the present composition. As a third illustrative example, when cured, the present composition may be capable of withstanding more than 4 pulls; alternatively more than 10 draws; alternatively more than 20 draws; alternatively more than 50 draws; alternatively more than 100 draws; or, alternatively, more than 200 draws. 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-bending, durability, and elasticity properties described herein. 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 in the technique that is both durable and elastic.

[0054] The present composition described so far can be combined with a pre-gel and/or promotion pack to form an adhesive composition particularly suitable for spraying onto an object and forming a sealant resistant to temperature and pressure changes associated with autoclaving under vacuum.

[0055] The pregel may comprise styrene, a clay composition and one or more additives. The pregel styrene 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 herein. The clay composition of the pregel comprises a composition in which 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 herein. For example, the clay composition may comprise nanoclay, an example available from the Neutrino Corporation (Tehran, Iran) under the trade name Cloisite® 10A.

[0056] As an illustrative method for making this composition, styrene and methyl methacrylate are added together and heated to approximately 80°F. A clay composition is then slowly and incrementally added to the mix and subjected to high shear mixing. When no clumping or minimal clumping is present, the mix is ready for further processing. The mixture is then combined with styrene and the present composition is subjected to high shear mixing 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 high shear mixing for 10 minutes total or per additive, depending on the additive introduced.

[0057] In embodiments where the present composition is combined with a pre-gel and/or promotion pack, the total composition may have one or more of the following characteristics: gel time of approximately 75 minutes; viscosity 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 the 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 it may contain amounts of other dicarboxylic acids or polycarboxylic acids which 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 the addition of cyclopentadiene or dicyclopentadiene. The addition of one or more additional resins to the present composition should not affect the ability of the composition to adhere to the substrates identified herein.

[0059] The core coating 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, 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 herein in various ways. The substrate can be a raw printed object or an object that has been machined to some extent. As a first illustrative example, the hand-mixed material (dressing and raw material in appropriate proportions, properly mixed in a cup or bucket) can be applied with a squeegee, roller, trowel, spatula, paint stick, brush or any other mechanical means that facilitates fully printing 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 setting can be used to extrude the properly started casing material into the ridges of the object. Depending on the size, shape and number of grooves present on the surface of the substrate, a combination of the first and second illustrative examples can be used most effectively, substantially representing a third exemplary application method. In cases of very large or deep grooves, it may be necessary to use a vibratory power source to ensure that the adhesive coating material completely fills the grooves in the surface of the substrate without the adhesive coating material containing air gaps.

[0060] In 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 the allowed to cure, and then another layer of the main wrap vinyl ester resin, 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 in the surface of the substrate. In these embodiments, it is preferred to allow the cured material to reach a temperature within approximately 10°F of the initial substrate surface temperature before another layer of the present composition is applied. Application and subsequent curing of the adhesive coating, when applied to the surface of a substrate, may result in an exothermic reaction. Therefore, a cooling period is required to obtain optimal 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 has fully cured, the object can be smoothed and/or shaped as needed, following standard processing techniques (eliminating sharp edges, etc.).

[0061] The average thickness of the adhesive coating on the surface of the substrate can range 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 to another layer of adhesive coating as the case may be), wherein the cured adhesive coating shows no or minimal evidence of thermal dimensional changes. One skilled in the art would readily appreciate what no or minimal evidence of thermal dimensional changes represents. For example, no or minimal evidence of thermal dimensional changes means that the human eye 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 smaller than 0.10mm, smaller than 0.05mm; 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 obviates the need for significant post-cure processing, the adhesive coating can be finished using conventional means of painting, sanding and/or polishing. When finished, the surface of the object shows no or minimal evidence of thermal dimensional changes as defined in this document.

[0064] In application methods where the present composition is being employed as a sealant, particularly in combination with a pre-gel and/or promotion pack, 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 an additional 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, the adhesive coating comprising a core coating vinyl ester resin; and (c) curing the adhesive coating. The method may further comprise (d) cooling the cured adhesive coating to within 10°F of the initial temperature of the substrate; (e) applying the adhesive coating; and (f) curing the adhesive coating applied in step (e). Steps (d) through (e) can be repeated as needed until the desired thickness of the adhesive coating or sealant is achieved. In preferred embodiments, each application of the adhesive to the substrate results in an average adhesive coating thickness 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 herein. 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 embodiments, forming step (a) is an additive manufacturing method, preferably large scale additive manufacturing methods.

[0066] The method of manufacturing a mold or prototype may further comprise applying paint or other sealant to the adhesive coating.

[0067] Turning now to the figure in which an embodiment of the present composition is applied to a substrate in a manner described herein to form an object, particularly an article of manufacture. Although the figure discloses one embodiment 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 those embodiments.

[0068] FIG. 1 shows a schematic diagram, in cross section, of a polymer substrate 1, the surface of which has been covered by the present composition to form an adhesive coating 2. Coating 2 further contains core coating particles 3. Substrate 1 has an as-manufactured surface 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 profile of the surface 5 of the substrate 1, as described further details in this document. It will be appreciated that Coating 2 can be applied in more than one coat and it will be further appreciated that, in general, the surface profile of subsequent coatings will be progressively smaller (i.e. the surface becomes smoother as more coats are applied). applied).

[0069] While specific embodiments have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to these details can be developed in light of the general teachings of the disclosure. In particular, the present composition described in this document can be used in many different ways and in different applications, not necessarily involving objects made by additive manufacturing. Accordingly, the disclosure presented herein is intended to be illustrative only and not limiting in scope and is to be given the full extent of the appended claims and any equivalents thereof.

EXAMPLES

[0070] Example 1. Durability. The durability of the present composition was tested by evaluating the number of pulls 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 tradename Plástico de Reparo 3 PiloGrip®. Comparator B is a commercially available product from Valvoline (Lexington, KY) sold under the trade name PlioGrip® Finishing Cream. Comparator C is a commercially available product from Valvoline (Lexington, KY), sold under the trade name Panel 60 PlioGrip®. Comparator D is a commercially available product from Clausen (Fords, NJ) sold under the trade name Z-Glas Comparator E is a commercially available product from 3M (St. Paul, MN) sold under the trade name EZ Flexible Parts Repair Adhesive sand. Comparator F is a commercially available product from 3M (St. Paul, MN) sold under the trade name Dent Filling Compound Body Filler. In this test, each adhesive coating was applied to carbon fiber filled ABS and the failure of its adhesive or cohesive properties was evaluated. Table 3.

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

[0072] Example 2. Membership. Adhesion of the present composition was tested in accordance with ASTM D4541, which is incorporated herein by reference in its entirety. Briefly, the adhesive composition is applied to the back of a cart, which is then placed on a substrate for testing. After the proper curing conditions, as set forth in each product's data sheet, a band saw or cutter was used to cut around the carriage through the coating to or just into the substrate. Then, manual pressure was exerted through the use of a PosiTest adhesion tester, commercially available from DeFelsko (Ogdensburg, NY). The pressure that resulted in 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 noted in Table 4 differ only in viscosity due to the use of a different monomer in the composition. Table 4.

[0073] The above results show that both embodiments of the present composition adhere to the substrate significantly better than the commercially available silicone adhesive. Furthermore, the foregoing results show that the present composition adheres to the substrate significantly better than a composition containing only a core coating vinyl ester resin. From these results, it is shown that the components act in a synergistic and surprising effect to achieve the reported adhesion properties.

[0074] Example 3. Elasticity. The present composition was tested for elasticity in accordance with ASTM D638, which is incorporated herein by reference in its entirety. Briefly, the cured adhesive composition is placed between a fixed member and a movable member held by grippers. The movable member is then moved away 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:

[0075] The foregoing results show that the present composition is more elastic than one 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 herein, particularly the adhesion and durability properties described in Examples 1 and 2. EMBODIMENTS

[0076] The foregoing description describes, illustrates and exemplifies one or more particular embodiments 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 one skilled in the art to understand these 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 the present disclosure is intended to cover all such embodiments that may fall within the scope of the appended claims, literally or under the doctrine of equivalents. The present disclosure notes that various embodiments are disclosed herein, at least including: A. A composition comprising a core coating vinyl ester and a 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 foregoing embodiment, wherein the core coating 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 actual composition. A.3. The composition of any foregoing 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 of the foregoing embodiments, 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 foregoing embodiment, 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 more preferably 0.1 to 15% of the total weight of the present composition. B. A composition comprising a first part comprising a core coating vinyl ester and a second part comprising a urethane acrylate. B.1. The composition of B, wherein 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 coating vinyl ester comprises 60 to 95%; preferably 65 to 95%; more preferably 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.1.b.i. The composition of B.1.b., wherein the monomer comprises 10 to 80%; preferably 10 to 70%; and more 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 B-B.2.b.i. embodiment, further comprising a third part comprising a monomer. 8.3. The. The composition of B.3., wherein 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 foregoing embodiment, wherein the core coating 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. 8.4. The composition of any foregoing embodiment, wherein the urethane acrylate comprises 5 to 25%, 5 to 20%, 5 to 15% or 10 to 15% of the total weight of the composition. 8.5. The composition of any preceding embodiment, wherein the urethane acrylate comprises 40 to 80%, 50 to 70% or 60 to 70% of the total weight of the second part. 8.6. The composition of any foregoing 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 foregoing embodiment, wherein the vinyl ester resin is produced from bisphenol-A diglycidyl ether (DGEBA) and methacrylic acid. C.2. The composition of any foregoing embodiment, wherein the vinyl ester resin is produced from a reaction between glycidyl methacrylate and a multifunctional phenol. C.3. The composition of any foregoing embodiment, wherein the core cladding polymers are selected from polymerized versions of: butadiene; butadiene and styrene; butadiene, methyl styrene methacrylate; 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, butadiene, and styrene methacrylate; alkyl acrylate, alkyl methacrylate and glycidyl methacrylate; and alkylacrylate and alkylmethacrylate, preferably butadiene. C.4. The composition of any foregoing 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 foregoing embodiment, wherein the urethane acrylate is a reaction product of a diisocyanate, an -OH-functional molecule with an olefinic double bond, and an optional material containing mono-, di- or multifunctional OH. D.1.a. The composition of D.1., wherein the diisocyanate is aromatic or aliphatic. D.1.a.i. The composition of D.1. or D.1.a., wherein the diisocyanate is selected from diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (HDI), isophorone (IPDI) or a combination thereof. D.2. The composition of any foregoing embodiment, wherein the urethane acrylate has an average hydroxy content of 100 to 115. D.3. The composition of any foregoing embodiment, wherein the urethane acrylate has a carbamate binding 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 foregoing embodiment, wherein the urethane acrylate has a molecular weight of 600 to 5000, preferably 1500 to 3000. D.5. The composition of any foregoing embodiment, wherein the urethane acrylate has a viscosity of 4000 cps at 60°C. D.6. The composition of any of the foregoing embodiments, wherein the urethane acrylate comprises two or more attributes of embodiments D.2. through D.5. D.7. The composition of any foregoing embodiment wherein the urethane acrylate comprises three or more attributes of embodiments D.2. through D.5. E.1. The composition of any foregoing embodiment, wherein the monomer is selected from styrene, methyl methacrylate, vinyl toluene, hydroxymethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl methacrylate, hydroxy ethyl 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, triallyl 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; pentaerythlitol triacrylate; pentaerythritol tetraacrylate; ethoxylated bisphenol A diacrylate; hexane diol diacrylate; dipentaerythritol monohydroxypentaacrylate; neopentyl glycol diacrylate; neopentyl glycol dimethacrylate; and tris(2-hydroxyethyl)isocyanurate triacrylate; preferably styrene. E.2. The composition of any foregoing embodiment, wherein the composition further comprises a pregel. E.2.a. The composition of I.1., wherein the pregel 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 I.1 or I.1.a, wherein the pregel comprises styrene, a clay composition and one or more additives. F.1. The composition of any foregoing embodiment, wherein one or more additives are selected from an air release/wetting agent, rheology modifier, thixotropic synergist, inhibitor, initiator, catalyst, surfactant, filler and paraffin wax. F.1.a. The composition of F.1., wherein the inhibitor is selected from t-butyl catechol, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, copper naphthenate and triphenyl antimony; or a combination thereof. F.1.b. The composition of F.1., wherein the catalyst is selected from cobalt naphthenate, cobalt octoate, cobalt hydroxide, potassium octoate, potassium naphanate, a manganese salt, an iron salt, N, N - dimethylaniline and N,N-dimethyl-p-toluidine; or a combination thereof. F.1.c. The composition of F.1., wherein the rheology modifier is selected from fumed silica, clay, organo-treated clay, castor oil and a polyamide; or a combination thereof. F.1.d. The composition of F.1., wherein the air release/wetting agent is selected from polyacrylate, silicone and mineral oil; or a combination thereof. F.1.e. The composition of F.1., wherein the coloring agent is selected from iron oxide, carbon black and titanium oxide; or a combination thereof. F.1.g. The composition of F.1., wherein the filler material comprises an organic or inorganic filler material. F.1.g.i. The composition of F.1.g, wherein the organic filler material is selected from polyethylene, a crosslinked polyester, a crosslinked acrylic, a crosslinked urethane, abs, graphite and carbon fibers; or a combination thereof. F.1.g.ii. The composition of F.1.g., wherein the inorganic filler material is selected from calcium carbonate, clay, talc, wollastonite, fly ash, glass microballoons, zinc sulfate, nano clay, nano silica, nano zinc and glass fibers; or a combination thereof. G.1. The composition of any preceding 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.1.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, wherein the unsaturated polyester resin is selected from maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid and azelaic acid. G.1.a.iv. The composition of any modality G.1.a. to G.1.a.iii, wherein 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.1.a.iv, where the unsaturated polyester resin has been modified by cyclopentadiene or dicyclopentadiene. H.1. The composition of any foregoing embodiment, wherein when the composition is cured, the composition exhibits a heat deflection temperature greater than 140°F, preferably greater than 160°F; and most preferably, greater than 180°F. H.2. The composition of any foregoing 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., where the elongation is determined in accordance with ASTM D638. H.3. The composition of any prior embodiment, wherein the present composition may be capable of withstanding more than 4 pulls; preferably more than 10 tractions; more preferably, greater than 20 pulls; even more preferably, greater than 50 pulls; even more preferably, more than 100 pulls; and ideally 200+ pulls. H.4. The composition of any foregoing embodiment, wherein the composition is cured through the use of an organometallic compound, UV, electron beam, heat or other peroxide systems. 1. 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 coating vinyl ester resin. 11. The object of I, wherein the adhesive coating further comprises a urethane acrylate. 12. The object of I or I1, wherein the core coating vinyl ester resin, the first part of any foregoing embodiment, or the composition of any foregoing embodiment, has an average thickness greater than 0.08 inches. 13. The object of any embodiment I to I2, wherein the adhesive coating has an average thickness per layer of 0.025 to 0.25 inches, preferably 0.08 to 0.12 inches. 14. The object of any one of Embodiments I through I3, wherein the average thickness of the adhesive coating on the surface of the substrate 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 one of Embodiments I to I4, wherein 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 one of Embodiments I to I5, wherein the adhesive coating inhibits the entry of gas or liquid into the substrate. 17. The object of any one of Embodiments I to I6, wherein the adhesive coating fills voids, geometric imperfections, missing or broken granules, under-filled cavities, or contours or surface textures of the substrate. 18. The object of any embodiment I to I7, wherein the adhesive coating further comprises one or more crosslinking agents, curing agents, thixotropic agents, air release/wetting agents, coloring agents, inorganic fillers, organic fillers, light weight fillers, surfactants, inorganic nanoparticles, organic nanoparticles and combinations thereof. 19. The object of any one of embodiments I to I8, wherein the substrate comprises acrylonitrile-butadiene-styrene, polyphenylene sulfide, polypenylsulfone, 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 one of embodiments I to I10, wherein the adhesive composition adheres to the surface of the polymer body and forms a bond between the adhesive coating and the substrate, wherein the strength of the bond between the coating and the substrate is greater than 300 psi. 112. The object of any embodiment I to I11, wherein 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 embodiment I to I12, wherein the substrate has a surface profile of 1.0 to 10 mm; preferably 2 to 7.5 mm and most preferably 2.5 to 5.0 mm before addition of the composition. 114. The object of any embodiment I to I13, wherein the adhesive coating, when cured onto 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 0.03mm. 115. The object of any one of Embodiments I to I14, wherein the object is a polymer composite article. 116. The object of any one of Embodiments I to I15, in which the object or article composed of polymer is generated by means of an additive manufacturing method. 117. The object of any one of embodiments I to I16, in which the polymer composite object or article is produced through the large-scale additive manufacturing method. 118. The object of any embodiment I to I17, wherein the adhesive coating comprises a composition of any embodiment A to H4. 119. A method of manufacturing 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 coating vinyl ester resin; (c) curing the adhesive coating applied in (b). J1. The method of J, wherein the adhesive coating further comprises urethane acrylate. J2. The method of J or J1, wherein 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 embodiment J to J2, wherein the application step comprises spraying the adhesive coating onto the surface of the polymer body. J3.a. The method of J3, wherein the adhesive coating forms a layer having a thickness of 0.004 to 0.01 inches, preferably 0.006 to 0.005 inches. J3.b. The method of J3 of J3.a., wherein the adhesive composition further comprises a pregel and/or promoter pack as defined by any embodiment of E2 to E2.b. J4. The method of any one of Embodiments 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 embodiment J through J4, wherein the application step comprises applying the composition to achieve a layer of the composition greater than 0.08 inches thick. J6. The method of any modality J through J5, in which curing is performed using UV light, an electron beam, an organometallic compound, a peroxide, or heat. J7. The method of any embodiment J through J6, wherein curing is accomplished by heating the substrate to a temperature of 50 to 350° C. J8. The method of any embodiment J to J7, wherein when the adhesive coating is cured, the adhesive coating exhibits a heat deflection temperature greater than 140°F; preferably greater than 160°F; and most preferably, greater than 180° F. J9. The method of any one of Embodiments J through J8, the method further comprising: (d) cooling the cured adhesive coating to within 10°F of the initial surface temperature of the substrate; (e) applying an additional layer of the adhesive coating; and (f) curing at least one layer of the adhesive coating applied in step (e) and, optionally (g) repeating steps (d) through (f) until the desired average thickness of the adhesive coating is achieved. J10. The method of any one of Embodiments J to J9, wherein the object is a polymer composite article. J11. The method of any embodiment J to J10, wherein the polymer composite object or article is generated by means of an additive manufacturing method. J12. The object of any one of Embodiments J to J11, wherein the polymer composite object or article is produced through the large-scale additive manufacturing method. J13. The method of any embodiment J to J12, wherein the polymer composite object or article is a mold or prototype. J14.The method of any embodiment J to J13, wherein the adhesive coating comprises a composition of any embodiment A to H4.

Claims (14)

1. Composition, characterized by a first part comprising a vinyl ester resin core, in which the polymer of the core is dispersed throughout the vinyl ester resin, and a second part comprising a urethane acrylate, in which the ester resin core coating vinyl ester resin comprises from 60 to 95% of the total weight of the composition, where the first part and the second part are prepared separately and combined to arrive at the adhesive composition, and where the core coating vinyl ester resin comprises polymer of core cladding with an average diameter ranging from 50 to 350 nm. 2. Composition according to claim 1, characterized in that the core coating vinyl ester resin comprises 75 to 95% of the total weight of the composition. 3. Composition, according to any preceding claim, characterized in that the urethane acrylate comprises 2 to 25% of the total weight of the composition. Composition according to claim 1, characterized in that it further comprises one or more unsaturated polyester resins. 5. Composition according to claim 1, characterized in that the composition has a carbamate binding content of 0.1 to 10%. 6. Composition according to any one of the preceding claims, characterized in that when the composition is cured, the composition exhibits a heat deflection temperature greater than 60°C and/or the composition can elongate by more than 5%. 7. Polymer composite article, characterized in that it comprises: a substrate comprising a polymer body having a surface with a surface profile in the range of 1.0 to 10mm; and, an adhesive coating on the surface of the polymer body, wherein the adhesive coating comprises core coating vinyl ester resin, in which the core polymer is dispersed throughout the vinyl ester resin, and in which the adhesive coating has a profile of Finished surface of less than 0.10 mm. 8. Composite article according to claim 7, characterized in that the adhesive coating further comprises a urethane acrylate and, optionally, one or more additives. 9. Composite article, according to claim 7 or 8, characterized in that the adhesive coating, when cured, has an average thickness greater than 2.0 mm. 10. Composite article, according to any one of claims 7 to 9, characterized in that the substrate comprises acrylonitrile butadiene styrene, polyphenylene sulfide, polyphenylsulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid or combinations thereof , each of which may optionally be reinforced with glass fibers, carbon fibers, bamboo or combinations thereof. 11. Composite article according to any one of claims 7 to 10, characterized in that the bond strength between the surface of the substrate and the adhesive coating after curing of the adhesive coating is at least 300 psi. 12. Composite article according to any one of claims 7 to 11, characterized in that the adhesive coating after the adhesive coating is cured has a finished surface profile of less than 0.10 mm. 13. Method for manufacturing a polymer composite article, characterized in that it comprises: (a) forming a substrate comprising a polymer body having a surface with a surface profile in the range of 1.0 to 10mm; (b) applying an adhesive coating to the surface of the polymer body, wherein the adhesive coating comprises the vinyl ester resin core, in which the core polymer is dispersed throughout the vinyl ester resin, and (c) curing the coating adhesive, wherein the adhesive coating has a finished surface profile of less than 0.10mm. 14. Method according to claim 13, characterized in that it further comprises: (d) cooling the cured adhesive coating to 5.6 °C of the initial temperature of the surface of the substrate; (e) applying an additional layer of the adhesive coating; (f) curing the adhesive coating applied in step (e); and optionally, (g) repeating steps (d) - (f) until the desired average thickness of the adhesive coating is achieved.

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