JP2020516762A5 - - Google Patents

Description

Summary The present disclosure relates to a composition comprising a core-shell vinyl ester resin and urethane acrylate. The core-shell vinyl ester resin may comprise 25-95% of the total mass of the composition and / or may contain a core-shell polymer having an average diameter of 50-350 nm. Urethane acrylicate can make up 2-25% of the total mass of the composition.
The composition may optionally further contain a monomer, one or more additives, and / or one or more unsaturated polyester resins. A particularly suitable monomer is styrene or a derivative thereof. Suitable additives include cross-linking agents, hardeners, thixotropic agents, air bleeding / wetting agents, colorants, air bleeding, inorganic or organic fillers, light fillers, surfactants, inorganic or organic nanoparticles, or a combination thereof. Can be mentioned.
The composition may have a carbamic acid binding content of 0.1-10%; it exhibits a thermal deformation temperature higher than 140 ° F (60 ° C); and / or the composition can stretch more than 5%.
The present disclosure further relates to a polymer composite made by addition manufacturing, comprising a polymer body having a surface and an adhesive coating containing a core-shell vinyl ester resin or the present composition of a core-shell vinyl ester resin and urethane acrylate. .. Polymer composites are made of substrates, the substrate type of which is acrylonitrile butadiene styrene, polyphenylene sulfide, polypenyl sulfone, polyether sulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid, or a combination thereof. obtain. These substrate types can be reinforced with, but not limited to, glass fiber, carbon fiber, bamboo, or a combination thereof.

When the adhesive coating is applied to the polymer composite, it may be applied in such a way that the composition has an average thickness greater than 0.08 inch (2.03 mm) on the surface of the substrate. As soon as it cures, the adhesive coating adheres to (1) the surface of the substrate; (2 the bond strength between the adhesive coating and the surface of the substrate is ^{greater than 300 psi (2.07 × 10 6} Pa); and / or ( 3) After curing, the adhesive coating can have a finished surface profile of less than 0.10 mm.
The disclosure further relates to a method of making a polymer composite, eg, a mold or prototype, using the composition to form a substrate containing a polymer having a surface; (b) core-shell vinyl ester. The present invention relates to a method comprising applying an adhesive coating containing a resin to the surface of a polymer body; and curing the adhesive coating applied in (c) and (b). The coating process can be accomplished through the use of squeegees, rollers, trowels, spatulas, paint sticks, paint brushes, or other mechanical means. Separately, the coating process could be accomplished by spraying the composition onto the object using a nebulizer. The result of the spraying process is a layer of adhesive coating with a thickness greater than 0.08 inches (2.03 mm), which can achieve the desired properties.
In some cases, multiple application of the adhesive coating may be required. In these cases, the pre-applied adhesive coating should cool within 10 ° F (5.6 ° C) of the initial temperature of the substrate surface. Then it can be cured by performing additional application of adhesive coating onto the adhesive coating prior to application.
The disclosure can be better understood from the detailed description below when read with the accompanying drawings. The figure is not always drawn to the correct scale.

Shown is the composition applied to the surface of a substrate as an adhesive coating or sealant by the methods disclosed herein to form a finished article.

In embodiments, the composition adheres to a substrate having a surface profile in the range 1.0-10 mm; or 2-7.5 mm; or 2.5-5.0 mm.
When the composition is applied as an adhesive coating or sealant to an object with a rough or uneven surface and cured, it results in an object that is impermeable to gas or liquid or substantially impermeable to gas or liquid. In other words, the use of the composition prevents the ingress of gas or liquid into the substrate of the object.
When used as an adhesive coating or sealant, the composition has been found to withstand standard and experimental thermal cycles without showing any internal defects on the surface of the substrate or without losing the vacuum seal. Although not constrained by any particular theory, the ability to withstand these thermal changes without deformation is at least partially due to the elongation properties of the composition.

In embodiments, the composition also functions to fill all print imperfections common to objects made by additive manufacturing when used as an adhesive coating or sealant. An unrestricted list of common defects includes voids, geometric imperfections, vanishing or breaking beads, under-fill cavities and surface contour / texture / decomposition issues. As a result of this function, the use of this composition results in an object with a receptive smooth surface in the final finish (eg, painting). The object is ideal for use as a mold or prototype.
The composition contains a core-shell vinyl ester resin and urethane acrylate. As used herein, "core-shell vinyl ester resin" means vinyl ester resin and core-shell polymer, with the core-shell polymer dispersed throughout the vinyl ester resin. An exemplary vinyl ester is disclosed in WO 1997/043339, which is hereby incorporated by reference in its entirety. The resin is sometimes called "reinforced vinyl ester resin". The most widely known and used vinyl ester resins are produced from the bisphenol A diglycidyl ether (DGEBA) and methacrylic acid. Typically, the reaction is catalyzed with an amine salt or triphenylphosphine at a temperature of about 120 ° C. for 4-5 hours. 90-95% methacrylic acid reacts to form vinyl ester. Styrene can be added to reduce the viscosity during synthesis. Separately, glycidyl methacrylate can be reacted with a polyfunctional phenol to form a vinyl ester resin.

The core-shell vinyl ester resin, the first portion of the composition, or the composition of any of the above embodiments can be used in several ways that will be readily apparent to those skilled in the art. For example, the voids of the substrate can be filled with the core-shell vinyl ester resin, the first portion of the composition, or the composition in several ways as the adhesive coating described herein. The substrate may be an unprocessed printed object or an object machined to some extent. As a useful example for the first explanation, squeegees, rollers, trowels, spatulas, paint sticks, paint brushes, or coating materials are hand-mixed materials (curable raw materials that are accurately mixed in a cup or bucket in the proper ratio). Can be applied by any mechanical means that facilitates pressing completely into the void. As a useful example for the second description, the spray tip can be removed from the sprayer without removing the static mixer. This structure can then be used to extrude a properly evoked coating material into the void of the object. Depending on the size, shape and number of voids present on the surface of the substrate, a combination of examples useful for the first and second explanations can be used up to maximum effectiveness, which is substantially the third exemplary application. It becomes a method. For very large or deep voids, adhesive coating material without containing air voids, adhesive coating material may need to use the vibrational energy source to fill completely reliably voids of the substrate surface.

In the embodiment, the composition is applied to the surface of the substrate and cured, and then the core-shell vinyl ester resin, the first portion of the composition, or another layer of the composition is applied to the cured layer of the adhesive coating. In an additional manner, the core-shell vinyl ester resin, the first portion of the composition, or the composition can be applied to the substrate surface as an adhesive coating. This method may be repeated until the desired surface is obtained. This coating method is particularly preferred when large voids are present on the surface of the substrate. In these embodiments, it is preferable to bring the cured material to a temperature within about 10 ° F (5.6 ° C) of the initial temperature of the substrate surface before applying another layer of the composition. When applied to the surface of the substrate, application of the adhesive coating and subsequent curing can result in an exothermic reaction. Therefore, cooling time is required to obtain the optimum physical properties of the adhesive coating. Each layer of adhesive coating may be applied if the average thickness of each layer is in the range of 0.025 to 0.25 inches (0.635 to 6.35 mm); or 0.08 to 0.12 inches (2.03 to 3.05 mm). When the coating is completely cured, the object can be smooth and / or the shape required by standard processing techniques (such as sharp edge removal).

The average thickness of the adhesive coating on the surface of the substrate is 0.05 to 0.50 inches (1.27 to 12.7 mm); or 0.1 to 0.45 inches (2.54 to 11.4 mm); or 0.1 to 0.45 inches (2.54 to 11.4 mm) to achieve the performance described herein. , 0.15 to 0.40 inches (3.81 to 10.1 mm); or 0.20 to 0.40 inches (5.08 to 10.2 mm); or 0.20 to 0.35 inches (5.08 to 8.89 mm); or 0.20 to 0.30 inches (5.08 to 7.62 mm) Range; or; can be about 0.25 inch (6.35 mm); or 0.25 inch (6.35 mm).
In a preferred embodiment, the cured adhesive coating is applied to the surface of the substrate (or, in some cases, to another layer of the adhesive coating). This cured adhesive coating shows no or minimal evidence of thermal dimensional change. Those skilled in the art will readily admit that they show no or minimal evidence of thermal dimensional change. For example, the absence or minimal evidence of thermal dimensional change means that the human eye cannot see any peaks or valleys present in the cured adhesive coating. As another example, the absence or minimal evidence of thermal dimensional change corresponds to a finished surface profile of less than 0.10 mm, less than 0.05 mm; or less than 0.04 mm; or less than 0.03 mm. ..
The adhesive composition exhibits self-leveling properties, which avoids the need for significant post-curing processing, but with a paint, sanding, and / or buff finish. The adhesive coating can be completed using the usual means of (buffing). Upon completion, the surface of the object shows no or minimal evidence of thermal dimensional change as specified herein.
In coating methods where the composition is used as a sealer, especially in combination with pregels and / or promotional packages, the composition is sprayed onto the substrate in a single or series of coatings to 0.004 to 0.01 inches (0.102 to 0.254 mm). Layers in the range of 0.006 to 0.008 inches (0.152 to 0.203 mm) can be obtained. After each application, the coating is cured at room temperature for 1 hour and then post-cured at 120 ° C. for an additional hour. When the composition is used as a sealer, the composition is particularly suitable for withstanding a thermal cycle.

This composition is a method for producing a mold or a prototype, in which (a) a substrate containing a polymer having a surface is formed; (b) an adhesive coating containing a core-shell vinyl ester resin is applied to the surface of the polymer. Can be used in methods involving the application of; and (c) curing the adhesive coating. This method further comprises (d) cooling the cured adhesive coating within 10 ° F (5.6 ° C) of the initial temperature of the substrate; (e) applying the adhesive coating; and (f) step (f). It may include curing the adhesive coating applied in e). Steps (d)-(e) can be repeated as needed until the desired thickness of the adhesive coating or sealer is obtained. In a preferred embodiment, each application of adhesive to the substrate results in an average thickness of adhesive coating greater than 0.08 inch (0.203 mm). The adhesive coating may further include urethane acrylate. The adhesive coating may include any embodiment of the composition described herein. After applying the adhesive coating and continuing to cure, the surface profile of the adhesive coating is less than the initial surface profile of the substrate surface. In the embodiment, the forming step (a) is an addition manufacturing method, preferably a large-scale addition manufacturing method.
The method of making a mold or prototype may further include applying a paint or another sealant to the adhesive coating.

Next, consider a diagram in which one embodiment of the present composition is applied to a substrate by the method described herein to form an object, particularly a manufactured product. Although the figure discloses one embodiment of the composition applied to a substrate to form an object, one of ordinary skill in the art will recognize that the teachings of the present disclosure are not limited to these embodiments.
FIG. 1 shows a schematic cross-sectional view of the polymer substrate 1, the surface of which is covered with the present composition to form an adhesive coating 2. Coating 2 further contains core-shell particles 3. The substrate 1 has an as-made surface 4 with a characteristic surface profile 5. Since the coating 2 has some degree of self-leveling, the outer surface 6 of the coating has a surface profile 7 that is substantially less than the surface profile 5 of the substrate 1, as largely detailed herein. It will be found that more coatings 2 can be applied than one coating, and more generally the surface profile of successive coatings will gradually decrease (ie, the surface will become smoother as more coatings are applied).
Having described the specific embodiments in detail, one of ordinary skill in the art will appreciate that various modifications and alternatives to the details can be developed in light of the teachings of the present disclosure. In particular, the compositions described herein can be used in a number of different methods and applications that do not necessarily involve objects made by additive manufacturing. Therefore, the disclosure herein is for illustration purposes only and is intended to be unrestricted in its scope and is intended to give the full scope of the appended claims and any equivalent thereof.

Example 1. Durability. The durability of the composition was tested through an assessment of the number of pulls the adhesive coating could withstand before the coating broke. The results of this analysis are shown in Table 3. Comparator A is a commercial product of Valvoline (Lexington, KY) sold under the trade name PiloGrip® Plastic Repair 3. Comparator B is a commercial product of Valvoline (Lexington, KY) sold under the trade name PlioGrip® Finishing Cream. Comparator C is a commercial product from Valvoline (Lexington, KY) sold under the trade name PlioGrip® Panel 60. Comparator D is a commercial product of Clausen (Fords, NJ) sold under the trade name Z-Glas. Comparator E is a commercial product of 3M (St. Paul, MN) sold under the trade name EZ sand Flexible Parts Repair Adhesive. Comparator F is a commercial product of 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 its adhesion or deterioration of adhesive properties was evaluated.

I. A polymer body having a surface; and an object comprising an adhesive coating on the surface of the polymer body containing a core-shell vinyl ester resin.
I1. An object of I whose adhesive coating further contains urethane acrylate.
I2. The core-shell vinyl ester resin, the first portion of any preceding embodiment, or the composition of any preceding embodiment has an average thickness greater than 0.08 inch (2.03 mm), I or I1. Object.
I3. Any one of embodiments I-2, wherein the adhesive coating has an average thickness of 0.025 to 0.25 inches (0.635 to 6.35 mm), preferably 0.08 to 0.12 inches (2.03 to 3.05 mm) per layer. object.
I4. The average thickness of the adhesive coating on the substrate surface is 0.05 to 0.50 inches (1.27 to 12.7 mm); preferably 0.1 to 0.45 inches (2.54 to 11.4 mm); more preferably 0.15 to 0.40 inches (3.81 to 3.81 to). 10.1 mm); more preferably 0.20 to 0.40 inches (5.08 to 10.2 mm); even more preferably 0.20 to 0.35 inches (5.08 to 8.89 mm); optimally 0.20 to 0.30 inches (5.08 to 7.62 mm). , Any one of embodiments I-3.
I5. The object of any one of embodiments I-4, wherein when the adhesive coating is applied to the surface of the polymer and cured, the object is impermeable to gas or liquid or substantially impermeable.
I6. An object of any one of embodiments I-5, wherein the adhesive coating prevents the ingress of gas or liquid into the substrate.
I7. An object of any one of embodiments I-6, wherein the adhesive coating fills the voids, geometric imperfections, vanishing or breaking beads, fill cavities, or surface contours or textures of the substrate.
I8. Adhesive coatings include one or more cross-linking agents, hardeners, thixotropes, air bleeders / wetting agents, colorants, inorganic fillers, organic fillers, light fillers, surfactants, inorganic nanoparticles, organic nanoparticles, And any one of embodiments I-7, further comprising a combination thereof.
I9. Any one of embodiments I-8, wherein the substrate comprises acrylonitrile butadiene styrene, polyphenylene sulfide, polypenylsulfone, polyether sulfone, polyethylene terephthalate, polybutylene terephthalate, polylactic acid, or a combination thereof. One object.
I10. An object of any one of embodiments I-9, wherein the substrate is reinforced with glass fiber, carbon fiber, bamboo, or a combination thereof.
I11. The adhesive composition adheres to the surface of the polymer to form a bond between the adhesive coating and the substrate, and the bond strength between this coating and the substrate is ^{greater than 300 psi (2.07 × 10 6} Pa). , Any one of embodiments I-10.
I12. Any one of embodiments I-11, wherein the surface of the polymer has a first surface profile and the surface of the cured coating has a second surface profile less than the first surface profile. object.
I13. The object of any one of embodiments I-12, wherein the substrate has a surface profile of 1.0 to 10 mm; preferably 2 to 7.5 mm, more preferably 2.5 to 5.0 mm prior to addition of the composition.
I14. When the adhesive coating cures on the surface of the polymer, 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; optimally less than 0.03 mm An object of any one of embodiments I-13 having a finished surface profile.
I15. An object of any one of embodiments I-14, wherein the object is a polymeric composite.
I16. An object of any one of embodiments I-15, wherein the object or polymer composite is produced by an addition manufacturing process.
I17. An object of any one of embodiments I-16, wherein the object or polymer composite is produced by a large-scale additive manufacturing process.
I18. An object of any one of embodiments I-17, wherein the adhesive coating comprises the composition of any one of embodiments A-H4.

J. Below:
(a) Forming a substrate containing a polymer with a surface;
(b) Applying an adhesive coating containing core-shell vinyl ester resin to the surface of the polymer body;
(c) A method of manufacturing an object, which comprises curing the adhesive coating applied in (b).
J1. J's method, where the adhesive coating further contains urethane acrylate.
J2. The method of J or J1, wherein the coating process comprises applying the composition by squeegee, roller, trowel, spatula, paint stick, paint brush, or other mechanical means.
J3. The method of any one of embodiments J-2, wherein the coating step comprises spraying an adhesive coating onto the surface of the polymer body.
J3.a. The method of J3, wherein the adhesive coating forms a layer with a thickness of 0.004 to 0.01 inches (0.102 to 0.254 mm), preferably 0.006 to 0.005 inches (0.152 to 1.27 mm).
J3.b. The method of J3 or J3.a., wherein the adhesive composition further comprises the pregel and / or promotional package according to any one of E2 to E2.b.
J4. The method of any one of embodiments J to J3.b, wherein the adhesive coating is applied and cured, and then another layer of the adhesive coating is applied to this cured layer.
J5. The method of any one of embodiments J-4, wherein the coating step comprises applying the composition to obtain a layer of the composition having a thickness greater than 0.08 inch (2.03 mm).
J6. The method of any one of embodiments J-5, wherein the curing is performed using UV light, an electron beam, an organometallic compound, a peroxide, or heat.
J7. The method of any one of embodiments J-6, wherein the curing is performed by heating the substrate at a temperature of 50-350 ° C.
J8. Once the adhesive coating has hardened, the adhesive coating has a heat above 140 ° F (60 ° C), preferably above 160 ° F (71 ° C), even more preferably above 180 ° F (82 ° C). Any one of embodiments J-7 that indicates the deformation temperature.
J9. The method is further below:
(d) Cool the cured adhesive coating within approximately 10 ° F (5.6 ° C) of the initial temperature of the substrate surface;
(e) Apply an additional layer of adhesive coating; and
(f) Curing at least one layer of the adhesive coating applied in step (e), and optionally.
(g) The method of any one of embodiments J-8, comprising repeating steps (d)-(f) until the desired average thickness of the adhesive coating is obtained.
J10. The method of any one of embodiments J-9, wherein the object is a polymeric composite.
J11. The method of any one of embodiments J-10, wherein the object or polymer composite is produced by an addition manufacturing process.
J12. The method of any one of embodiments J-11, wherein the object or polymer composite is produced by a large-scale additive manufacturing process.
J13. The method of any one of embodiments J-12, wherein the object or polymer composite is a mold or prototype.
J14. The method of any one of embodiments J-13, wherein the adhesive coating comprises the composition of any one of embodiments A-H4.