CN110506092B

CN110506092B - Adhesive composition and method for coating objects

Info

Publication number: CN110506092B
Application number: CN201780089595.4A
Authority: CN
Inventors: R.E.斯皮尔斯; R.斯普林菲尔德; M.阿克曼; A.拉弗朗布瓦兹; M.A.马修斯; R.J.保尔; S.L.沃克斯
Original assignee: Tru-Design LLC; Polynt Composites USA Inc
Current assignee: Tru-Design LLC; Polynt Composites USA Inc
Priority date: 2017-04-14
Filing date: 2017-04-14
Publication date: 2023-03-14
Anticipated expiration: 2037-04-14
Also published as: BR112019021114B1; MY193513A; EP3609970A4; JP7453906B2; JP2020516762A; WO2018190876A1; BR112019021114A2; CN110506092A; AU2017409719A1; EP3609970A1; KR102300463B1; CA3059186A1; AU2017409719B2; KR20200037131A; NZ757870A

Abstract

An adhesive composition comprising a core shell vinyl ester and a urethane acrylate suitable for application to a rough or uneven surface of a substrate to provide a smooth surface. The adhesive composition of the invention is particularly suitable for coating large objects made by additive manufacturing to form molds or prototypes.

Description

Adhesive composition and method for coating an object

Joint research protocol

Aspects of the invention are made by or on behalf of the parties to the federated research agreement listed below. The joint research agreement is valid on or before the date the aspects of the invention are made and the aspects of the invention are made due to activities conducted 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.

Background

The present application relates generally to adhesive compositions for use as coatings or sealants for objects. In particular, the composition of the invention may be used as a coating or sealant for objects having a rough or uneven surface (e.g. objects made by additive manufacturing).

Additive manufacturing, also known as three-dimensional printing, has become increasingly popular and is now widely used in the industry for manufacturing objects. However, objects made by additive manufacturing have a rough surface and are therefore not suitable for many intended applications, such as for use as a mould or prototype. Accordingly, there is a need for improved compositions and methods to improve the surface of objects made by additive manufacturing.

Previous attempts to address the rough surface of these objects have included grinding the object to produce a smooth surface, and then coating (painting) the object to produce the final product. However, grinding objects is very time consuming, generates a large amount of dust, which often causes problems due to its carbon or other fiber content, and limits the usefulness of the additive manufacturing method in real world applications. Furthermore, coating failures are common because the coating (paint) cannot withstand the expansion and contraction of the object.

Existing coating compositions for objects made by additive manufacturing, in particular large objects, often lack sufficient adhesion to common substrates, such as Acrylonitrile Butadiene Styrene (ABS), polyphenylene sulfide (PPS), and the like. In addition, existing coating compositions fail due to expansion and/or contraction of the substrate under various conditions. Therefore, there is a need for a coating composition that can sufficiently adhere to ordinary substrates and give objects a smooth surface.

Large objects made by additive manufacturing also face many other technical challenges, as detailed in part by Int J Adv Manuf technol. (29Sept 2016) of Sudbury et al, the entire contents of which are incorporated herein by reference. These challenges include, but are not limited to, the build-up of coatings or adhesive sealants and their cracking. Accordingly, there is a need for a coating composition that can overcome known problems associated with large objects made by additive manufacturing.

Objects made by additive manufacturing completed by known compositions and methods lack durability. Molds made of conventional materials can withstand tensile forces greater than 10, greater than 50, or greater than 100. However, a mold comprising an object made by additive manufacturing can only withstand tensile forces of less than 5 or less than 10. Accordingly, there is a need for coating compositions that can withstand the mechanical forces associated with standard use of molds.

The object made by additive manufacturing may undergo further processing to add components to the object. These objects are subjected to autoclaving under vacuum. The compositions of the prior art have not been able to withstand the temperature and pressure variations associated with hot pressing under vacuum. Accordingly, there is a need for a coating composition that can withstand the temperature and pressure variations associated with finished (finishing) objects made by additive manufacturing.

Disclosure of Invention

The present disclosure relates to compositions comprising a core shell 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 a core shell polymer having an average diameter of 50 to 350 nm. The urethane acrylate may comprise 2 to 25% by weight of the total composition.

The composition of the present invention may optionally further comprise monomers, one or more additives and/or one or more unsaturated polyester resins. Particularly suitable monomers are styrene or derivatives thereof. Suitable additives include cross-linking agents, curing agents, thixotropic agents, air release/wetting agents, colorants, air release, inorganic or organic fillers, lightweight fillers, surfactants, inorganic or organic nanoparticles, or combinations thereof.

The urethane linking group (linking) content of the composition of the invention may be from 0.1 to 10%; exhibits a heat deflection temperature (heat deflection temperature) greater than 140 ° F; and/or the composition may be extensible greater than 5%.

The present disclosure further relates to polymer composite articles, preferably prepared by additive manufacturing, comprising a polymeric form having a surface and an adhesive coating comprising a core shell vinyl ester resin or a composition of the core shell vinyl ester resin of the present invention and a urethane acrylate. The polymer composite article is made from a substrate, wherein the substrate type can be acrylonitrile butadiene styrene, polyphenylene sulfide, polyphenylene sulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid, or combinations thereof. These substrate types may be reinforced with materials including, but not limited to, fiberglass, carbon fiber, bamboo (bamboo), or combinations thereof.

When the adhesive coating is applied to the polymer composite article, the application may be such that the average thickness of the composition on the surface of the substrate is greater than 0.08 inches. 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 300psi; and/or (3) after the adhesive coating is cured, the surface profile of the finished product (finished) can be less than 0.10mm.

The present disclosure is still further directed to a method of making a polymer composite article, such as a mold or prototype, using the composition of the present invention, comprising: (a) Forming a substrate comprising a polymeric form having a surface; (b) Applying an adhesive coating to a surface of the polymeric form, wherein the adhesive coating comprises a core shell vinyl ester resin; and (c) curing the adhesive coating applied in (b). The applying step may be accomplished by using a doctor blade, roller, trowel, spatula, bar, brush, or other mechanical means. Alternatively, the applying step may be accomplished by spraying the composition onto the object using a sprayer. The result of the applying step may be a layer of adhesive coating greater than 0.08 inches thick to achieve the desired properties.

In some cases, the adhesive coating must be applied multiple times. In these cases, the previously applied adhesive coating should cool to within 10 ° F of the initial temperature of the surface of the substrate. The adhesive coating may then be additionally applied to the previously applied adhesive coating and allowed to cure.

Drawings

The disclosure is better understood from the following detailed description when read in conjunction with the accompanying drawings. These features are not necessarily drawn to scale.

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

Detailed Description

The adhesive composition of the present invention can be used as an adhesive composition for filling voids of an object having a rough or uneven surface existing on some substrates. The adhesive compositions of the invention are also useful as sealants capable of withstanding the temperature and pressure changes common to objects comprising certain substrates. Both objects may be produced by additive manufacturing methods.

The compositions and methods of use disclosed herein are designed for use with objects having rough or uneven surfaces. As used herein, "object" includes an article of manufacture, preferably a polymer composite article, and more preferably a polymer composite article made by additive manufacturing, and most preferably a polymer composite article made by large scale additive manufacturing. In a preferred embodiment, the object may be a mold or a prototype. These objects may include a variety 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, and the like, or combinations thereof. One skilled in the art will appreciate that other similar substrates may be used with the compositions of the present invention.

In embodiments, the inventive composition adheres to a substrate with a surface topography in the range of 1.0 to 10mm; alternatively, 2 to 7.5mm; or 2.5 to 5.0mm.

When the composition of the invention is applied as an adhesive coating or sealant to an object having a rough or uneven surface and allowed to cure, the result is that the object is impermeable or substantially impermeable to gases or liquids. In other words, the use of the composition of the present invention inhibits the ingress of gas or liquid into the substrate of the object.

When used as an adhesive coating or sealant, the compositions of the present invention have been shown to withstand standard and experimental thermal cycling without showing potential defects in the substrate surface or loss of vacuum sealability. Without being bound by any particular theory, it is believed that the ability to withstand these thermal changes without deforming is due at least in part to the elongation properties of the compositions of the present invention.

In embodiments, the present compositions, when used as an adhesive coating or sealant, also function to fill all printing defects common in objects made by additive manufacturing. A non-limiting list of common defects includes voids, geometric defects, missing or broken beads, underfilled cavities, and surface contour/texture/resolution issues. As a result of this effect, objects having a smooth surface that can receive a final finish (e.g., coating) are obtained using the compositions of the present invention. These objects are very suitable for use as molds or prototypes.

The compositions of the present invention comprise a core shell vinyl ester resin and a urethane acrylate. As used herein, "core-shell vinyl ester resin" means a vinyl ester resin and a core-shell polymer, wherein the core-shell polymer is dispersed throughout the vinyl ester resin. An exemplary vinyl ester is disclosed in WO 1997/043339, the entire contents of which are incorporated herein by reference. Such resins are also known as "toughened vinyl ester resins". The most widely known and used vinyl ester resins are prepared from diglycidyl ether of bisphenol a (DGEBA) and methacrylic acid. Typically, the reaction is catalyzed using an amine salt or triphenylphosphine at a temperature of about 120 ℃ for 4 to 5 hours. 90 to 95% of the methacrylic acid reacts to form vinyl esters. Styrene may be added to reduce viscosity during synthesis. Alternatively, glycidyl methacrylate can be reacted with a multifunctional phenol to form a vinyl ester resin.

In accordance with the present disclosure, core shell polymers dispersed in vinyl ester resins are typically prepared by controlled emulsion polymerization during which the composition of the monomer feed is varied in order to achieve the desired compositional changes in the structure of the core shell polymer. While many core shell polymers having a variety of properties can be used, core shell polymers suitable for use in the compositions of the present invention typically have a core that is rubbery at ambient conditions and prepared by polymerizing monomers such as butadiene and alkyl acrylates. By "rubbery under ambient conditions" is understood that the core of the core-shell polymer has a Tg below ambient temperature. Preferred core shell polymers include, but are not limited to, the following polymeric forms: butadiene; butadiene and styrene; butadiene, methyl methacrylate and styrene; butadiene, alkyl methacrylates and alkyl acrylates; butadiene, styrene, alkyl acrylates, alkyl methacrylates and methacrylic acid; butadiene, styrene, alkyl acrylates, alkyl methacrylates, methacrylic acid and low molecular weight polyethylene (as flow modifiers); butyl acrylate and methyl methacrylate; alkyl methacrylates, butadiene and styrene; alkyl acrylates, alkyl methacrylates, and glycidyl methacrylates; and alkyl acrylates and methacrylates. The core shell polymer may have an average diameter of 50 to 350nm; alternatively, 100 to 300nm; alternatively, 150 to 250nm; alternatively, about 200nm; alternatively, 200nm. Particularly preferred core shell polymers for use in the compositions of the present invention are core shell polymers that incorporate butadiene as the core component. The preferred shell component is poly (methyl methacrylate) (PMMA). The core shell polymer may be amine terminated butadiene nitrile rubber (ATBN) nanoparticles. One suitable core-shell polymer is a polybutadiene core with a poly (methyl methacrylate co-styrene) shell. The core shell polymer may optionally be disposed within a carrier resin. The carrier resin may be a general bisphenol epoxy resin or a derivative thereof known to those skilled in the art. For example, preferred carrier resins are diglycidyl ethers of bisphenol A and extended forms thereof. The carrier resin may be a diepoxy resin (diepoxy), such as Novalac.

In embodiments, the core shell vinyl ester resin comprises from about 25 to about 95% of the total weight of the composition of the present invention; alternatively, about 25 to 95%; alternatively, 50 to 95%; alternatively, 60 to 95%; or 75 to 95%.

As used herein, "urethane acrylate" means the reaction product of a diisocyanate, an-OH functional molecule having an olefinic double bond, and optionally a mono-, di-, or multifunctional-OH containing material. One exemplary urethane acrylate for use in the compositions of the present invention is disclosed in U.S. patent nos. 4,485,226 and 4,507,458, which are incorporated herein by reference in their entirety. As used herein, "diisocyanate" means any type of aromatic, aliphatic, cycloaliphatic, and aromatic-aliphatic polyisocyanate having two or more isocyanate groups per molecule; including dimers and trimers. Exemplary aromatic polyisocyanates include diphenylmethane diisocyanate (MDI) and Toluene Diisocyanate (TDI). Exemplary aliphatic polyisocyanates include Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI). "OH-functional molecules having olefinic double bonds" may include partial esters of polyols with acrylic acid or methacrylic acid, for example ethylene glycol monoacrylate or monomethacrylate, 1,2-or 1,3-propylene glycol monoacrylate or monomethacrylate, 1,4-butylene glycol monoacrylate or monomethacrylate, 1,6-hexanediol monoacrylate or monomethacrylate, trimethylolpropane diacrylate, glycerol diacrylate, pentaerythritol triacrylate and the mono (N-methylolacrylamide) -ethers and mono- (N-methylolmethacrylamide) -ethers of ethylene glycol, propylene glycol, butylene glycol, hexanediol and neopentyl glycol. "mono-, di-or polyfunctional OH-containing materials" may include polyfunctional alcohols, such as diols of 2 to 8 carbon atoms, e.g., ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, triols, e.g., glycerol, trimethylolpropane and hexanetriol, pentaerythritol, and the like; or polyether polyols prepared by reacting 1 molecule of an alcohol with 1 to 50, preferably 15 to 30 molecules of ethylene oxide or propylene oxide. The polyester polyols can include the reaction product of the polycondensation of a polyacid (e.g., adipic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid) with a polyol (e.g., 1,4-butanediol, 1,3-butanediol, ethylene glycol, diethylene glycol, propylene glycol, 1,2-propanediol, dipropylene glycol, 1,6-hexanediol, and neopentyl glycol).

In embodiments, the urethane acrylate has one or more of the following attributes: a carbamate linkage content of 0.1 to 10%, alternatively, 0.5 to 5%, alternatively, 0.5 to 4%, alternatively, 0.5 to 3%; a nominal molecular weight of 600 to 5000, preferably 1500 to 3000; the viscosity was about 4000cps @60 ℃.

In embodiments, the urethane acrylate comprises from about 2 to about 25% of the total weight of the composition of the present invention; alternatively, 2 to 25%; or 5 to 20%.

The compositions of the present invention may further comprise one or more additives selected from the group consisting of air release/wetting agents, rheology modifiers, thixotropic synergists, inhibitors, initiators, catalysts, surfactants, fillers, and waxes. The compositions of the present invention may comprise more than one additive of the same type (e.g., one or more fillers) or a combination of different types of additives (e.g., at least one catalyst and at least one surfactant).

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

The composition of the present invention may further comprise a monomer. Exemplary monomers include, but are not limited to, styrene, methyl methacrylate, vinyl toluene, hydroxymethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, alpha-methyl styrene, and divinyl benzene. Other exemplary monomers include o-methylstyrene, m-methylstyrene, p-methylstyrene, methyl acrylate, t-butylstyrene, diallyl phthalate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate; ethoxylated trimethylolpropane triacrylate; glycerol propoxy 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 dimethacrylate; butanediol diacrylate; butanediol dimethacrylate; pentaerythritol triacrylate; pentaerythritol tetraacrylate; ethoxylated bisphenol a diacrylate; hexanediol diacrylate; dipentaerythritol monohydroxypentaacrylate; neopentyl glycol diacrylate; neopentyl glycol dimethacrylate; and tris (2-hydroxyethyl) isocyanurate triacrylate. In a preferred embodiment, the monomer is styrene or one of its derivatives.

The monomer may comprise from 0.1 to about 40% of the total weight of the composition of the present invention; alternatively, 0.1 to 40%; alternatively, 0.1 to 30%; or 0.1 to 20%.

The compositions of the present invention may comprise a multi-part composition, wherein the parts are prepared separately and then combined to give the compositions of the present invention. In these embodiments, the compositions of the present invention comprise a first part comprising a core shell vinyl ester resin; and a second part comprising a urethane acrylate. The compositions of the present invention may optionally further comprise a third part comprising a monomer as described herein.

The first part may comprise from about 25 to about 95% of the total weight of the composition of the present invention; alternatively, 25 to 95%; alternatively, 30 to 95%; alternatively, 50 to 90%; alternatively, 55 to 85%; alternatively, 60 to 80%; alternatively, 65 to 75%; alternatively, 70 to 75%.

The second part may comprise from about 2 to about 25% of the total weight of the composition of the present invention; alternatively, 2 to 25%; alternatively, 5 to 20%; alternatively, 5 to 15%; alternatively, 10 to 15%.

The third part may comprise from about 1 to about 75% of the total weight of the composition of the present invention; alternatively, 1 to 75%; alternatively, 2 to 40%; alternatively, 10 to 30%; alternatively, 10 to 20%; alternatively, 15 to 20%.

The first part may comprise a core shell vinyl ester resin as described herein. The first part may comprise a reaction product of an epoxy resin and methacrylic acid or a derivative thereof, wherein the core shell polymer is distributed in the epoxy resin. The epoxy resin may comprise a bisphenol a/epichlorohydrin derived liquid epoxy resin. For example, one suitable bisphenol a/epichlorohydrin derived liquid epoxy resin is d.e.r available from Dow (Midland, MI 48674). ^TM 331. The other kind isA suitable bisphenol A/epichlorohydrin derived liquid epoxy resin is EPON available from Hexion Specialty Chemicals (Columbus, OH 43215) ^TM A Resin 828. In embodiments, the bisphenol A/epichlorohydrin derived liquid epoxy resin is a resin having an epoxy equivalent (g/eq) of 185-192, a viscosity at 25 ℃ of 110 to 150P, a density at 25 ℃ of 9.7lbs/gal having a vapor pressure at 77 ℃ of about 0.03mm Hg, a refractive index at 25 ℃ of about 1.5, and/or a specific heat of about 0.5BTU/lb/° F. In embodiments, the bisphenol a/epichlorohydrin derived liquid epoxy resin is a resin having an epoxide equivalent weight (g/eq) of 182-192, a percent epoxide of 22.4 to 23.6%, an epoxide group content of 5200 to 5500, a viscosity of 11000 to 14000mPa-s, and/or a density of about 1.16g/ml at 25 ℃. In a preferred embodiment, the epoxy resin is a mixture of two or more bisphenol a/epichlorohydrin derived liquid epoxy resins described herein.

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

The first portion of the resulting core shell vinyl ester resin may comprise from about 60 to about 95% of the total weight of the first portion; alternatively, 60 to 95%; alternatively, 65 to 95%; alternatively, 70 to 95%; alternatively, 75 to 95%.

In embodiments, the first part may further comprise monomers described herein, which may comprise from about 10 to about 80% of the total weight of the first part; alternatively, 10 to 70%; alternatively, 20 to 40%; alternatively, 25 to 35%. In a preferred embodiment, the monomer is styrene or one of its derivatives.

The first part may further comprise one or more additives. Particularly suitable additives are stabilizers which promote shelf life or stability of the first part and/or ultimately the entire composition of the invention. One suitable additive for the first part is hydroquinone available from Sigma-Aldrich co., LLC (st. Louis, MO 63103). Hydroquinone, when present, constitutes less than 1% of the total weight of the first part; alternatively, less than 0.05%; alternatively, 0.01 to 0.05%; alternatively, about 0.03%; alternatively, 0.03%. 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% of the total weight of the first part; alternatively, less than 0.05%; alternatively, 0.001 to 0.015%; alternatively, about 0.01%; alternatively, 0.01%. 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% of the total weight of the first part; alternatively, less than 0.5%; alternatively, 0.2 to 0.4%. 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% of the total weight of the first part; alternatively, 0.2 to 0.6%; alternatively, 0.3 to 0.5%. Another suitable additive for the first part is 2-hydroxyethyl methacrylate available from Sigma-Aldrich co., LLC (st. Louis, MO 63103). When present, 2-hydroxyethyl methacrylate comprises about 1 to about 10% of the total weight of the first part; alternatively, 1 to 10%; alternatively, 2 to 8%; alternatively, 3 to 6%; alternatively, about 5%; alternatively, 5 wt%.

The urethane acrylate may comprise about 40 to about 90% of the total weight of the second part; alternatively, 40 to 90%; alternatively, 50 to 90%; alternatively, 60 to 90%; alternatively, 70 to 90%.

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

In one embodiment, the composition of the present invention comprises the components listed in table 1.

Table 1:

components	Percentage of the total composition
		Core-shell vinyl ester resins	25–95％
Urethane acrylate
		2–25％
Monomer			0–40％
	Additive agent	0–40％

The additives indicated in table 1 may be added directly to the individual components or to the overall composition as described in the multi-part disclosure. In another embodiment, the compositions of the present invention may comprise the components listed in table 2.

Table 2:

components	Percentage of the total composition
		Core-shell vinyl ester resins	75–95％
Urethane acrylate
		5–25％
Styrene (meth) acrylic acid ester			0–20％
	Additive agent	0–10％

The additives indicated in table 2 may be added directly to the individual components or to the overall composition as described in the multi-part disclosure.

In yet another embodiment, the compositions of the present invention may comprise the components listed in table 3.

Table 3:

the core shell vinyl ester resin or first part can be prepared according to the following procedure. A clean, dry glass reactor equipped with a stirrer, a dry air jet and a heating mantle was charged with bisphenol a epoxy resin and core shell polymer dispersed in the epoxy resin and mixed. The mixture was then heated to about 115 ℃. Tetramethylammonium chloride and bisphenol a were added slowly and the temperature was maintained between 115 and 120 ℃ until the epoxy value stabilized. At this point the monomers, hydroquinone and 2,4,6-tris (dimethylaminomethyl) phenol may be added and mixed. Methacrylic acid was then added gradually and mixed over a two hour period, maintaining the temperature at about 115 ℃ until the acid number stabilized. The mixture was then cooled to room temperature. Additives as disclosed herein can be added to the cooled mixture to form the first part.

The urethane acrylate or second part may be prepared according to the following procedure. In a moisture free clean glass reactor equipped with a dry air sparge and a stirrer, toluene diisocyanate and triphenylantimony were added to the reactor and stirring was started. The dry air sparge was then started and hydroxyethyl acrylate was added over a two hour period, maintaining the temperature less than 130 ° F. The mixture was then held at 125 ° F for 30 minutes. Then methyl hydroquinone was added and mixed. The polyol was then added gradually over an hour at 130 ° F. When the isocyanate reaction was complete, 100ppm of methyl hydroquinone and monomer were added and mixed. The mixture was then cooled to room temperature. Additives as disclosed herein can be added to the cooled mixture to form the second part.

The compositions of the present invention can be made using a high shear mixer (e.g., a ribbon blender). In embodiments, the core shell vinyl ester resin or first part is added with the urethane acrylate or second part and mixed together by a high shear mixer at a temperature of less than 120 ° F for about 3 minutes. The monomer or third part and/or one or more additives are then added to the mixture and mixed to obtain the desired physical properties. In a preferred embodiment, the first part and the second part are added together and mixed by the high shear mixer at a temperature in the range of from less than 65 to 85 ° F for about three minutes. Monomers and additives can then be added to the mixture to obtain optimal physical properties. For example, monomers and additives may be added until the inventive composition exhibits one or more of the following characteristics: viscosity of 10,000 to 30,000cPs @20rpm; viscosity of 16,000 to 20,000cPs @20rpm; a thixotropic index greater than 3; a thixotropic index greater than 4; the gelation time at room temperature is 6 to 10min; the density is 0.50 to 1.0g/cm ³ (ii) a Or a density of 0.70 to 0.80g/cm ³ . Particularly suitable additives to achieve these properties include air release/wetting agents, one or more rheology modifiers, thixotropic synergists, one or more inhibitors, one or more initiators, one or more catalysts, one or more surfactants, one or more fillers, paraffin waxes.

When present, the air release/wetting agent is selected from the group consisting of polyacrylates, silicones, mineral oils, or combinations thereof. When present, the rheology modifier is selected from fumed silica; clays, particularly organically treated clays; castor oil; polyamides, and combinations thereof. When present, the catalyst is selected from the group consisting of cobalt naphthenate, cobalt octoate, cobalt hydroxide, potassium octoate, potassium naphthenate, manganese salts, iron salts, n.n-dimethylaniline, n.n-dimethyl-p-toluidine. In a preferred embodiment, the inventive composition uses a combination of two catalysts, otherwise described herein as a catalyst and a co-catalyst. In a preferred embodiment, one or more catalysts and co-catalysts are added to the inventive composition prior to application for desired curing properties, depending on the intended use. When present, the inhibitor may be a chemical capable of extending the shelf life and/or extending the gel time of the composition of the present invention. Exemplary inhibitors include, but are not limited to, t-butyl catechol, hydroquinone, methyl hydroquinone, monomethyl ether of hydroquinone, copper naphthenate, triphenylantimony. When present, the filler may be one or more organic fillers, one or more inorganic fillers, or a combination thereof. Exemplary organic fillers include, but are not limited to, low profile additives, polyethylene, crosslinked polyesters, crosslinked acrylics, crosslinked urethanes, absorbents (abs), graphite, graphene, carbon nanotubes, and carbon fibers. Exemplary low profile additives include polyvinyl acetate, polystyrene, polyethylene, and the like. Exemplary inorganic fillers include, but are not limited to, calcium carbonate, clay, talc, wollastonite, fly ash, glass microspheres, zinc sulfate, nanoclay, nanosilica, and glass fibers. When present, the colorant can be any standard pigment additive known to alter the color of the resin composition. Exemplary colorants include, but are not limited to, iron oxide, carbon black, and titanium oxide.

Curing of the compositions of the present invention may be facilitated by the use of organometallic compounds, UV, electron beam, heat, or other peroxide systems known in the art. In a preferred embodiment, when a peroxide system is employed, the peroxide system may be a peroxide or hydroperoxide, preferably at a concentration of 0.5 to 4%. Exemplary 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 cured by heating, the compositions of the present invention may be cured at temperatures of from 50 to 350 ℃ depending on the initiator used. When cured, the compositions of the present invention may exhibit one or more properties that are particularly noteworthy for the uses described herein. As a first illustrative example, the present compositions may exhibit greater than 140 ° F when cured; alternatively, greater than 160 ° F; or, a heat distortion temperature greater than 180 ° F. As a second illustrative example, when cured, the inventive composition may have an elongation of greater than 5%; alternatively, greater than 6%; alternatively, greater than 7%, as determined according to the test method set forth in ASTM D638, which is incorporated herein by reference in its entirety. As will be understood by those skilled in the art, this elongation measure is illustrative of the elasticity of the compositions of the present invention. As a third illustrative example, the present compositions may be capable of withstanding greater than 4 pulls when cured; alternatively, greater than 10 pulls; alternatively, greater than 20 pulls; alternatively, greater than 50 pulls; alternatively, greater than 100 pulls; alternatively, more than 200 pulls. One skilled in the art will appreciate that the pull metric is a standard value for determining durability. An experimental protocol for determining pull number is disclosed in example 1 herein. In a preferred embodiment, the compositions of the present invention, when cured, exhibit a combination of heat distortion, durability, and elastic properties as described herein. One skilled in the art will unexpectedly find that the compositions of the present invention exhibit a combination of these properties. For example, it is difficult in the art to design compositions that are both durable and elastic.

The compositions of the present invention described thus far may be combined with a pre-gel and/or booster kit to form an adhesive composition particularly suitable for spraying onto an object, and to form a sealant that is resistant to the temperature and pressure changes associated with hot pressing under vacuum.

The pre-gel may comprise styrene, a clay composition (ingredient), and one or more additives. The pre-gelled styrene may comprise from about 10 to about 40% by weight of the total composition; alternatively, 10 to 40 percent; alternatively, 15 to 35%; alternatively, 15 to 30%; alternatively, 15 to 25%; alternatively, 20-25%. The one or more additives may include one or more additives described herein. The pre-gelled clay composition (ingredient) includes compositions in which clay is present. Those skilled in the art will appreciate the types of clay compositions suitable for use in the applications described herein. For example, the clay composition may include a nanoclay, examples of which may be under the trade name

10A was obtained from Neutrino Corporation (Tehran, iran).

As an illustrative method of making the composition, styrene and methyl methacrylate are added together and heated to about 80 ° F. The clay composition is then added slowly and incrementally to the mixture and subjected to high shear mixing. When no or only little agglomeration is present, the mixture is ready for further processing. The mixture was then combined with styrene and the composition of the present invention and subjected to high shear mixing for 10 minutes. If one or more additives are employed as the chemical curing agent, such as cobalt octoate or cobalt hydroxide, the chemical curing agent may be added to the mixture and subjected to high shear mixing for an additional 10 minutes. Finally, and optionally, depending on the additives introduced, one or more additives are added to the mixture and high shear mixing is performed for a total of 10 minutes or 10 minutes for each additive.

In embodiments where the compositions of the present invention are combined with a pre-gel and/or booster kit, the overall composition may have one or more of the following characteristics: gel time about 75min; a viscosity of 75-100cps at 25 deg.C; and/or the percentage of non-volatile matter is 20-40%; preferably 30-40%; or optimally 30-35%.

The compositions of the present invention may 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 may be any resin prepared by polyesterification of a polyol with a polycarboxylic acid, at least a portion of which contains ethylenic unsaturation. Typically useful unsaturated polyester resins contain as the polyol any low molecular weight diol 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 di-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. The polyesters may also be modified by, for example, the addition of cyclopentadiene or dicyclopentadiene. The addition of one or more additional resins to the compositions of the present invention should not affect the ability of the compositions to adhere to the substrates identified herein.

The inventive compositions of the core shell vinyl ester resin, the first part of the inventive composition, or any of the previously described embodiments may be used in a variety of ways that will be apparent to those skilled in the art. For example, the core shell vinyl ester resin, the first part of the inventive composition, or the inventive composition may be used as an adhesive coating described herein to fill voids in a substrate in a variety of ways. The substrate may be a raw printed object, or an object that has been machined to some extent. As a first illustrative example, the hand-mixed materials (curing agent and raw materials properly mixed in a cup or bucket in a suitable ratio) may be applied with a spatula, roller, trowel, spatula, bar, brush, or any mechanical means that would assist in completely pressing the coating material into the void. As a second illustrative example, the nozzle tip may be removed from the spray coating apparatus without removing the static mixer. This configuration can then be used to extrude the appropriately initiated coating material into the voids of the object. Depending on the size, shape and number of voids present in the surface of the substrate, a combination of the first and second illustrative examples may be used to maximize efficacy, essentially representing the third exemplary application method. In the case of large or deep voids, it may be necessary to use a source of vibrational energy to ensure that the adhesive coating completely fills the voids in the surface of the substrate, while the adhesive coating does not contain air voids.

In embodiments, the core shell vinyl ester resin, the first part of the composition of the invention, or the composition of the invention may be applied as an additive to the surface of the substrate as an adhesive coating, wherein the composition of the invention is applied to the surface of the substrate, allowed to cure, and then another layer of the core shell vinyl ester resin, the first part of the composition of the invention, or the composition of the invention is applied over the cured adhesive coating layer. The process may be repeated until the desired surface is obtained. This application method is particularly preferred when large voids are present in the substrate surface. In these embodiments, the cured material is preferably brought to a temperature within about 10 ° F of the initial temperature of the surface of the substrate prior to application of another layer of the composition of the present invention. When applied to the surface of a substrate, the application and subsequent curing of the adhesive coating can result in an exothermic reaction. Therefore, a cooling time is required to achieve the best physical properties of the adhesive coating. Each layer of adhesive coating can be applied with an average thickness of 0.025 to 0.25 inches per layer; alternatively, 0.08 to 0.12 inches. Once the coating is fully cured, the object can be smoothed and/or shaped as desired according to standard machining techniques (elimination of sharp edges, etc.).

The average thickness of the adhesive coating on the surface of the substrate may be 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; about 0.25 inches; alternatively, 0.25 inches, to achieve the properties described herein.

In a preferred embodiment, a cured adhesive coating is applied to the surface of the substrate (or to another adhesive coating layer as the case may be), wherein the cured adhesive coating shows no or minimal signs of thermal dimensional change. One skilled in the art will readily understand what no or minimal evidence of thermal dimensional change is represented. For example, no or minimal evidence of thermal dimensional change means that the human eye is unable to identify any peaks or valleys present in the cured adhesive coating. As another example, no or minimal evidence of thermal dimensional change indicates a finished product surface topography of less than 0.10mm, less than 0.05mm; alternatively, less than 0.04mm; alternatively, less than 0.03mm.

While the adhesive composition exhibits self-leveling properties, which in turn avoids the need for significant post-cure treatment, conventional coating, sanding, and/or polishing methods can be used to finish the adhesive coating. Upon finishing, the surface of the object shows no or minimal signs of thermal dimensional change as defined herein.

In methods of using the present compositions as sealant applications, particularly in combination with a pre-gel and/or booster kit, the present compositions can be sprayed onto a substrate in a single or a series of applications to obtain a layer in the range of 0.004 to 0.01 inch, preferably 0.006 to 0.008 inch. After each application, the coatings were allowed to cure at room temperature for one hour and then post-cured at 120 ℃ for another hour. The compositions of the present invention are particularly well suited to withstand thermal cycling when used as sealants.

The composition of the present invention can be used in a method of making a mold or prototype comprising: (a) Forming a substrate comprising a polymeric form having a surface; (b) Applying an adhesive coating to a surface of the polymeric form, wherein the adhesive coating comprises a core shell vinyl ester resin; (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 an adhesive coating; and (f) curing the adhesive coating applied in step (e). Steps (d) through (e) may be repeated as necessary until the desired adhesive coating or sealant thickness is obtained. In a preferred embodiment, each application of the adhesive to the substrate results in an average thickness of the adhesive coating of greater than 0.08 inches. The adhesive coating may further comprise a urethane acrylate. The adhesive coating may further comprise any embodiment of the inventive composition described herein. After the adhesive coating is applied and subsequently cured, the surface topography of the adhesive coating is less than the original surface topography of the surface of the substrate. In an embodiment, the forming step (a) is a method of additive manufacturing, preferably a method of large scale additive manufacturing.

The method of making a mold or prototype may further comprise applying a coating or another sealant to the adhesive coating.

Turning now to the drawings, wherein one embodiment of the composition of the present invention is applied to a substrate in the manner described herein to form an object, particularly an article of manufacture. Although this figure discloses applying one embodiment of the composition of the present invention to a substrate to form an object, one of ordinary skill in the art will appreciate that the teachings of the present disclosure will not be limited to these embodiments.

Fig. 1 shows a schematic cross-sectional view of a polymeric substrate 1, the surface of the polymeric substrate 1 having been covered with a composition of the present invention to form an adhesive coating 2. The coating 2 further contains core-shell particles 3. The substrate 1 has a surface 4 thus produced with a characteristic surface topography 5. Because the coating 2 has a degree of self-leveling, the outer surface 6 of the coating has a surface topography 7 that is significantly less than the surface topography 5 of the substrate 1, as described in more detail herein. It will be appreciated that the coating 2 may be applied in more than one coating layer, and it will further be appreciated that, in general, the surface topography of subsequent coating layers will become progressively smaller (i.e., the surface becomes smoother as more coating layers are applied).

While specific embodiments have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. In particular, the inventive compositions described herein may be used in many different ways and in different applications, without necessarily involving objects made by additive manufacturing. Accordingly, the disclosure herein is to be considered as illustrative and not restrictive in scope, and the appended claims are to be accorded the full scope of equivalents thereof.

Examples

Example 1.And (4) durability. The durability of the compositions of the present invention was tested by evaluating the number of pulls that the adhesive coating can withstand before the coating fails. The results of this analysis are shown in Table 4. Control A is available under the trade name Valvoline (Lexington, KY)

Commercially available product of Plastic Repiair 3. Control B is available under the trade name Valvoline (Lexington, KY)

The product commercially available from Finishing team. Control C is available under the trade name Valvoline (Lexington, KY)

Commercially available product of Panel 60. Comparative D is a product commercially available from Clausen (Fords, NJ) under the trade name Z-Glas. Control E is a product commercially available from 3M (st. Paul, MN) under the trade name EZ sand Flexible Parts Repair Adhesive. Control F is a product commercially available from 3M (St. Paul, MN) under the trade name Dent Filling Compound Body Filler. In this test, each adhesive coating was applied to carbon fiber filled ABS and its adhesive or cohesive properties were evaluated for failure.

Table 4.

The foregoing results show that the compositions of the present invention are significantly longer lasting than the commercial alternatives.

Example 2.Adhesion. The compositions of the present invention were tested for adhesion according to ASTM D4541, which is incorporated herein by reference in its entirety. Briefly, the adhesive composition was applied to the back of a trolley (dolly) and then placed on a substrate for testing. After the appropriate curing conditions listed in the data sheet for each product, a hole saw or cutter was used to cut the coating around the trolley, either through to or just into the substrate. Manual pressure was then applied by using a PosiTest Pull-Off addition Tester commercially available from DeFelsko (Ogdensburg, NY). The pressure at which the adhesive composition failed is shown in table 5. The silicone adhesive used in this example is commercially available from Devco (Tulsa, OK) under the trade name S120. Examples shown in Table 5The viscosities of embodiment a and embodiment B differ only by the use of different monomers in the composition.

Table 5.

The foregoing results show that both embodiments of the inventive composition adhere significantly better to substrates than commercially available silicone adhesives. Furthermore, the foregoing results show that the inventive compositions adhere to substrates significantly better than compositions containing only the core shell vinyl ester resin. These results show that the components act with synergistic and unexpected effects to achieve the reported adhesion properties.

Example 3.And (4) elasticity. The compositions of the present invention were tested for elasticity according to ASTM D638, which is incorporated herein by reference in its entirety. In short, a cured adhesive composition is interposed between a movable member and a fixed member fixed by a jig. The movable member is then moved away from the stationary member in a controlled manner to apply elastic tension to the composition of the present invention. The test measures the maximum elongation, which is shown in table 6.

Table 6:

core-shell-only vinyl ester resins	Compositions of the invention
		5％	Greater than or equal to 8 percent

The foregoing results show that the compositions of the present invention are more elastic than one aspect of the compositions of the present invention. In view of the other physical properties described herein, particularly adhesion and durability as described in examples 1 and 2, one skilled in the art will readily appreciate that the compositions of the present invention have unexpected elasticity.

Detailed description of the preferred embodiments

The foregoing description describes, illustrates, and exemplifies one or more particular embodiments of an adhesive composition. This description is not provided to limit the disclosure to the embodiments described herein, but rather to explain and teach various principles that will enable one of ordinary skill in the art to understand these principles and with that understanding be applied in practice and not only to the embodiments described herein, as well as other embodiments conceivable in light of these principles. The scope of the disclosure is intended to cover all such embodiments as may come within the scope of the following claims, either literally or under the doctrine of equivalents. The present disclosure indicates that various embodiments are disclosed herein, including at least:

A. a composition comprising a core shell vinyl ester and a urethane acrylate.

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

A2. The composition of any preceding embodiment, wherein the core shell vinyl ester resin comprises from 25 to 95% of the total weight of the composition of the present invention; preferably 50 to 95%; more preferably 60 to 95%; or optimally 75 to 95%.

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

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

A.4.a.a.4 composition wherein the monomers comprise 0.1 to 40% by weight of the total composition of the invention; preferably 0.1 to 30%; and more preferably 0.1 to 20%.

A.5. The composition of any preceding embodiment, further comprising one or more additives.

A.a.a.5 composition wherein the one or more additives comprise 0.1 to 40% by weight of the total composition of the invention; preferably 0.1 to 20%; and more preferably 0.1 to 15%.

B. A composition comprising a first portion comprising a core shell vinyl ester and a second portion comprising a urethane acrylate.

The composition of B.1.B, wherein the first part comprises from 25 to 95% of the total weight of the composition of the invention; preferably 30 to 95%; more preferably 50 to 90%; and optimally 65 to 75%.

The composition of b.1.a.b or b.1. Wherein the core-shell vinyl ester comprises 60 to 95% of the total weight of the first part; preferably 65 to 95%; more preferably 70 to 95%; and optimally 75 to 95%.

The composition of b1.b.b or b.1.a., wherein the first part further comprises a monomer and/or one or more additives.

The composition of b.1.b.i.b.1.b., wherein the monomers comprise 10 to 80% of the total weight of the first part; preferably 10 to 70%; and more preferably 20 to 40%; and optimally 25 to 35%.

The composition of b.2.b or b.1. Wherein the second part comprises 2 to 25% of the total weight of the composition of the invention; preferably 5 to 20%; more preferably 5 to 15%; and optimally 10 to 15%.

A composition of b.2.a.b.2 wherein the urethane acrylate comprises 40 to 90% of the total weight of the second part; preferably 50 to 90%; more preferably 60 to 90%; and optimally 70 to 90%.

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

The composition of b.2.b.i.b.2.b., wherein the one or more additives aid in curing the composition and/or crosslinking components of the composition.

A composition according to any one of the embodiments of b.3.b to b.2.b.i. further comprising a third portion comprising a monomer.

The composition of b.3.a.b.3. Wherein the third part comprises 1 to 75% of the total weight of the composition of the invention; preferably 2 to 40%; more preferably 2 to 40%; still more preferably from 10 to 30%; and optimally 10 to 20%.

The composition of any preceding embodiment, wherein the core shell vinyl ester comprises 45 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 preceding 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.

B.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.

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

C.1. The composition of any preceding embodiment, wherein the vinyl ester resin is prepared from diglycidyl ether of bisphenol a (DGEBA) and methacrylic acid.

C.2. The composition of any preceding embodiment, wherein the vinyl ester resin is prepared from a reaction between glycidyl methacrylate and a multifunctional phenol.

C.3. The composition of any preceding embodiment, wherein the core shell polymer is selected from the following polymeric forms: butadiene; butadiene and styrene; butadiene, methyl methacrylate and styrene; butadiene, alkyl methacrylates and alkyl acrylates; butadiene, styrene, alkyl acrylates, alkyl methacrylates and methacrylic acid; butadiene, styrene, alkyl acrylates, alkyl methacrylates, methacrylic acid and low molecular weight polyethylene (as flow modifiers); butyl acrylate and methyl methacrylate; alkyl methacrylates, butadiene and styrene; alkyl acrylates, alkyl methacrylates, and glycidyl methacrylates; and alkyl acrylates and methacrylates, preferably butadiene.

C.4. The composition of any preceding embodiment, wherein the average diameter of the core shell polymer is from 50 to 350nm, preferably from 100 to 300nm, more preferably from 150 to 250nm; and most preferably 200nm.

A composition according to any of the preceding embodiments wherein the urethane acrylate is the reaction product of a diisocyanate, an-OH functional molecule having an olefinic double bond, and optionally a mono-, di-, or multifunctional-OH containing material.

The composition of d.1.a.d.1. Wherein the diisocyanate is aromatic or aliphatic.

The composition of d.1.a.i.d.1 or d.1.a. Wherein the diisocyanate is selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), or combinations thereof.

D.2. The composition of any preceding embodiment, wherein the average hydroxyl content of the urethane acrylate is 100 to 115.

D.3. The composition of any preceding embodiment, wherein the urethane acrylate has a urethane linkage content of 0.1 to 10%; preferably 0.5 to 5%; more preferably 0.5 to 4%; and optimally 0.5 to 3%.

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

D.5. The composition of any preceding embodiment, wherein the urethane acrylate has a viscosity of 4000cps at 60 ℃.

D.6. The composition of any preceding embodiment, wherein the urethane acrylate comprises two or more attributes of embodiments d.2. To d.5.

D.7. The composition of any preceding embodiment, wherein the urethane acrylate comprises three or more attributes of embodiments d.2. To d.5.

E.1. The composition of any preceding embodiment, wherein the monomer is selected from the group consisting of styrene, methyl methacrylate, vinyl toluene, hydroxymethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, alpha-methyl styrene, and divinyl benzene. Other exemplary monomers include o-methylstyrene, m-methylstyrene, p-methylstyrene, methyl acrylate, t-butylstyrene, diallyl phthalate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate; ethoxylated trimethylolpropane triacrylate; glycerol propoxy 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 dimethacrylate; butanediol diacrylate; butanediol dimethacrylate; pentaerythritol triacrylate; pentaerythritol tetraacrylate; ethoxylated bisphenol a diacrylate; hexanediol diacrylate; dipentaerythritol monohydroxypentaacrylate; neopentyl glycol diacrylate; neopentyl glycol dimethacrylate; and tris (2-hydroxyethyl) isocyanurate triacrylate; styrene is preferred.

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

E.2.A.i.1 wherein the pre-gel comprises 10 to 40% by weight of the total composition; preferably 15 to 35%; more preferably 15 to 30%; still more preferably 15 to 25%, and optimally 20 to 25%.

The composition of e.2.B.i.1 or i.1.A, wherein the pre-gel comprises styrene, a clay composition and one or more additives.

F.1. The composition of any preceding embodiment, wherein the one or more additives are selected from the group consisting of air release/wetting agents, rheology modifiers, thixotropic synergists, inhibitors, initiators, catalysts, surfactants, fillers, and paraffin waxes.

A composition according to f.1.a.f.1. Wherein the inhibitor is selected from the group consisting of tert-butyl catechol, hydroquinone, methyl hydroquinone, monomethyl ether of hydroquinone, copper naphthenate and triphenyl antimony; or a combination thereof.

The composition of f.1.b.f.1. Wherein the catalyst is selected from the group consisting of cobalt naphthenate, cobalt octoate, cobalt hydroxide, potassium octoate, potassium naphthenate, manganese salts, iron salts, N-dimethylaniline and N, N-dimethyl-p-toluidine; or a combination thereof.

The composition of f.1.c.f.1. Wherein the rheology modifier is selected from the group consisting of fumed silica, clay, organically treated clay, castor oil, and polyamide; or a combination thereof.

The composition of f.1.d.f.1. Wherein the air release/wetting agent is selected from the group consisting of polyacrylates, silicones, and mineral oils; or a combination thereof.

The composition of f.1.e.f.1. Wherein the colorant is selected from the group consisting of iron oxide, carbon black, and titanium oxide; or a combination thereof. F.1, wherein the filler comprises an organic or inorganic filler.

F.1.i.f.1.g of a composition wherein the organic filler is selected from the group consisting of polyethylene, cross-linked polyester, cross-linked acrylic, cross-linked urethane, absorbent, graphite and carbon fiber; or a combination thereof.

F.1.g. ii.f.1.g. wherein the inorganic filler is selected from calcium carbonate, clay, talc, wollastonite, fly ash, glass microspheres, zinc sulfate, nanoclay, nanosilica, 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.

The composition of g.1.a.g.1 wherein the one or more additional resins is one or more unsaturated polyester resins.

The composition of g.1.a.i.g.1.a. Wherein the unsaturated polyester resin is prepared by polyesterification of a polyol with a polycarboxylic acid.

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

The composition of any one of embodiments g.1.a.iii.g.1.a. To g.1.a.ii, wherein the unsaturated polyester resin is selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, and azelaic acid.

The composition of any one of embodiments g.1.a.iv.g.1.a. To g.1.a.iii wherein at least a portion of the unsaturated polyester resin contains ethylenic unsaturation.

The composition of any one of the embodiments g.1.a.v.g.1.a.iv, wherein the unsaturated polyester resin has been modified with cyclopentadiene or dicyclopentadiene.

H.1. The composition of any preceding embodiment, wherein the composition exhibits a surface roughness of greater than 140 ° F, preferably greater than 160 ° F; and more preferably greater than 180F.

H.2. The composition of any preceding embodiment, wherein the composition is extensible greater than 5%, preferably greater than 6%; more preferably greater than 8%.

H.2.a.h.2, wherein the elongation is determined according to ASTM D638.

H.3. The composition of any preceding embodiment, wherein the composition of the present invention can withstand greater than 4 pulls; preferably more than 10 pulls; more preferably greater than 20 pulls; still more preferably greater than 50 pulls; yet more preferably greater than 100 pulls; and optimally greater than 200 pulls.

H.4. The composition of any preceding embodiment, wherein the composition is cured by using an organometallic compound, UV, electron beam, heat, or other peroxide system.

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

I1.I, wherein the adhesive coating further comprises a urethane acrylate.

I or I1, wherein the average thickness of the core shell vinyl ester resin, the first part of any preceding embodiment, or the composition of any preceding embodiment is greater than 0.08 inches.

I3. The object of any of the embodiments I to I2, wherein the average thickness of each layer of the adhesive coating is from 0.025 to 0.25 inches, preferably from 0.08 to 0.12 inches.

I4. The object of any of the embodiments I-I3, wherein the average thickness of the adhesive coating on the surface of the substrate is from 0.05 to 0.50 inches; preferably 0.1 to 0.45 inches; more preferably 0.15 to 0.40 inches; still more preferably 0.20 to 0.40 inches; still more preferably 0.20 to 0.35 inches; and most preferably 0.20 to 0.30 inches.

I5. The object of any of the embodiments I to I4, wherein the object is impermeable or substantially impermeable to a gas or liquid when the adhesive coating is applied to the surface of the polymeric body and allowed to cure.

The object of any of the embodiments I to I5, wherein the adhesive coating inhibits the ingress of gas or liquid into the substrate.

The object of any one of embodiments I to I6, wherein the adhesive coating fills voids, geometric imperfections, missing or broken beads, underfilled cavities or surface contours or textures of the substrate.

The object of any of the embodiments I-I7, wherein the adhesive coating further comprises one or more crosslinkers, curing agents, thixotropic agents, air release/wetting agents, colorants, inorganic fillers, organic fillers, lightweight fillers, surfactants, inorganic nanoparticles, organic nanoparticles, and combinations thereof.

The object of any one of the embodiments I to I8, wherein the substrate comprises acrylonitrile butadiene styrene, polyphenylene sulfide, polyphenylene sulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid, or a combination thereof.

The object of any one of embodiments I-I9, wherein the substrate is reinforced with glass fibers, carbon fibers, bamboo, or a combination thereof.

The object of any of embodiments I to I10, wherein the adhesive composition adheres to a surface of the polymeric body and forms a bond between the adhesive coating and the substrate, wherein the bond strength between the coating and the substrate is greater than 300psi.

I12. The object of any one of the embodiments I to I11, wherein the surface of the polymeric form has a first surface topography and the surface of the coating after curing has a second surface topography that is less than the first surface topography.

I13. The object of any of the embodiments I to I12, wherein the surface topography of the substrate before addition of the composition is from 1.0 to 10mm; preferably 2 to 7.5mm and more preferably 2.5 to 5.0mm.

I14. The object of any of the embodiments I to I13, wherein the finished surface topography of the adhesive coating is less than 0.1mm when cured on the surface of the polymeric body; preferably less than 0.08mm; more preferably less than 0.05mm; still more preferably less than 0.04mm; and most preferably less than 0.03mm.

The object of any one of the embodiments I to I14, wherein the object is a polymer composite article.

I16. The object of any one of the embodiments I to I15, wherein the object or the polymer composite article is produced by an additive manufacturing process.

I17.i to I16, wherein the object or polymer composite article is prepared by a large scale additive manufacturing process.

The object of any of the embodiments I to I17, wherein the adhesive coating comprises the composition of any of the embodiments a to H4.

J. A method of manufacturing an object, comprising:

(a) Forming a substrate comprising a polymeric form having a surface;

(b) Applying an adhesive coating to a surface of the polymeric form, wherein the adhesive coating comprises a core shell vinyl ester resin;

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

The method of j1.j, wherein the adhesive coating further comprises a urethane acrylate.

J2. Or J1, wherein the applying step comprises applying the composition with a doctor blade, roller, trowel, spatula, bar, brush, or other mechanical means.

The method of any one of embodiments J3.J to J2, wherein the applying step comprises spraying the adhesive coating onto the surface of the polymeric body.

J3.A. 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.

The method of J3 of j3.b.j3.a., wherein the adhesive composition further comprises a pre-gel and/or an acceleration kit as defined in any one of the embodiments of E2 to E2.b.

The method of any one of embodiments j4.j to j3.b, wherein an adhesive coating is applied and cured, and then another layer of adhesive coating is applied to the cured layer.

The method of any one of embodiments J5.J to J4, wherein the applying step comprises applying the composition to obtain a layer of the composition having a thickness of greater than 0.08 inches.

The method of any one of embodiments J to J5, wherein curing is performed using UV light, electron beam, organometallic compound, peroxide, or heat.

The method of any one of embodiments J to J6, wherein curing is performed by heating the substrate at a temperature of 50 to 350 ℃.

The method of any of embodiments J to J7, wherein the adhesive coating exhibits greater than 140 ° F when the adhesive coating is cured; preferably greater than 160 ° F; and most preferably greater than 180F.

The method of any one of embodiments J to J8, wherein the method further comprises:

(d) Cooling the cured adhesive coating to within 10 ° F of the surface initiation temperature of the substrate;

(e) Applying an additional layer of adhesive coating; and

(f) Curing the at least one layer of adhesive coating applied in step (e), and optionally

(g) Repeating steps (d) through (f) until a desired average thickness of the adhesive coating is obtained.

The method of any one of embodiments J to J9, wherein the object is a polymer composite article.

The method of any one of embodiments J to J10, wherein the object or polymer composite article is produced by an additive manufacturing process.

The object of any one of embodiments J to J11, wherein the object or the polymer composite article is prepared by a mass additive manufacturing process.

The method of any one of embodiments J13.J to J12, wherein the object or polymer composite article is a mold or prototype.

The method of any one of embodiments J to J13, wherein the adhesive coating comprises the composition of any one of embodiments a to H4.

Claims

1. Use of a multi-part adhesive composition comprising a multi-part adhesive composition for filling all printing defects in an object made by additive manufacturing

A first part comprising a core shell vinyl ester resin, wherein the core shell polymer is dispersed throughout the vinyl ester resin, and

a second part comprising a urethane acrylate,

wherein the core shell vinyl ester resin comprises 60 to 95% of the total weight of the composition,

wherein the first part and the second part are prepared separately and combined to give the adhesive composition,

by core shell vinyl ester resin is meant both vinyl ester resin and core shell polymer wherein the core shell polymer is dispersed throughout the vinyl ester resin.

2. Use according to claim 1, wherein the core shell vinyl ester resin comprises 75 to 95% by weight of the total composition.

3. The use of claim 1, wherein the core shell vinyl ester resin comprises a core shell polymer having an average diameter of 50 to 350 nm.

4. Use according to claim 1, wherein the urethane acrylate constitutes from 2 to 25% of the total weight of the composition.

5. The use of claim 1, wherein the composition further comprises a third part comprising a monomer.

6. Use according to claim 1, wherein the composition further comprises one or more unsaturated polyester resins.

7. The use of claim 1, wherein the composition further comprises one or more additives.

8. The use of claim 7, wherein the one or more additives comprise a cross-linking agent, a curing agent, a thixotropic agent, an air release/wetting agent, a colorant, an inorganic or organic filler, a lightweight filler, a surfactant, or a combination thereof.

9. Use according to claim 8, wherein the inorganic or organic filler is an inorganic or organic nanoparticle.

10. The use of claim 1, wherein the composition, when cured, exhibits a heat distortion temperature of greater than 140 ° F and/or the composition is extensible by greater than 5%, as determined according to the test method set forth in ASTM D638.

11. A polymer composite article comprising:

a substrate comprising a polymeric body having a surface with a surface topography in the range of 1.0 to 10mm; and the combination of (a) and (b),

an adhesive coating on a surface of the polymeric body, wherein the adhesive coating comprises a core shell vinyl ester resin, wherein the core shell polymer is dispersed throughout the vinyl ester resin, and

wherein the surface appearance of the finished product of the adhesive coating is less than 0.10mm,

wherein the polymer composite article is produced by an additive manufacturing process.

12. The composite article of claim 11, wherein the adhesive coating further comprises a urethane acrylate and optionally one or more additives.

13. The composite article of claim 11, wherein the average thickness of the adhesive coating upon curing is greater than 0.08 inch.

14. The composite article of claim 11, wherein the substrate comprises acrylonitrile butadiene styrene, polyphenylene sulfide, polyphenylsulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid, or combinations thereof, each of which is optionally reinforced with glass fibers, carbon fibers, bamboo, or combinations thereof.

15. The composite article of claim 11, wherein the bond strength between the surface of the substrate and the adhesive coating is at least 300psi after the adhesive coating is cured.

16. A method of making a polymer composite article comprising:

(a) Forming a substrate comprising a polymeric body having a surface with a surface topography in the range of 1.0 to 10mm, wherein the forming step (a) is a method of additive manufacturing;

(b) Applying an adhesive coating to a surface of the polymeric form, wherein the adhesive coating comprises a core shell vinyl ester resin, wherein the core shell polymer is dispersed throughout the vinyl ester resin;

(c) And curing the adhesive coating, wherein the surface topography of the finished product of the adhesive coating is less than 0.10mm.

17. The method of claim 16, wherein the adhesive coating further comprises a urethane acrylate and optionally one or more additives.

18. The method of claim 16, wherein the substrate comprises acrylonitrile butadiene styrene, polyphenylene sulfide, polyphenylsulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid, or combinations thereof, each of which is optionally reinforced with glass fibers, carbon fibers, bamboo, or combinations thereof.

19. The method of claim 16, wherein the applying step comprises applying an adhesive coating to form a layer of the composition having a thickness greater than 0.08 inches.

20. The method of claim 16, 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 adhesive coating;

(f) Curing the adhesive coating applied in step (e); and optionally also (c) a second set of one or more of,

(g) Repeating steps (d) - (f) until a desired average thickness of the adhesive coating is obtained.

21. The method of claim 16, wherein the adhesive coating is applied by: the composition is applied by spraying an adhesive coating onto the surface of the polymeric body, or by applying with a doctor blade, roller, trowel, spatula, bar, or brush.