HK1169906B - Aliphatic moisture-curable resins, coating compositions, and related processes - Google Patents

Description

Aliphatic moisture-curable resins, coating compositions, and related methods

Technical Field

The present invention relates to moisture-curable aliphatic resins comprising polyisocyanate functional materials. The present invention also relates to coating compositions comprising moisture-curable, aliphatic resins containing polyisocyanate functional materials. The present invention also relates to methods of using moisture-curable, aliphatic resins and coating compositions comprising polyisocyanate functional materials.

Background

Compositions based on isocyanate chemistries have been found to be useful as components in coatings (e.g., paints, primers, etc.). Isocyanate-based coating compositions may include, for example, polyurethane coatings formed from resins containing components such as diisocyanates, polyisocyanates, and/or isocyanate reaction products. These resins can be cured by various mechanisms such that covalent bonds are formed between the resin components, thereby producing a crosslinked polymer network.

Moisture-curable (i.e., moisture-curable) coatings based on isocyanate-functional resins represent one class of isocyanate-based coating technologies. Isocyanate-based moisture-curable coatings generally comprise, for example, diisocyanates, polyisocyanates, and/or isocyanate reaction products having free isocyanate groups that can react with atmospheric moisture, thereby producing insoluble, higher molecular weight, crosslinked polyurethane networks that can form part of the cured coating. The term "polyurethane" as used herein refers to polymeric or oligomeric materials.

The curing process may include the reaction of free isocyanate groups with atmospheric water molecules to form a carbamic acid intermediate that decomposes into amine groups and carbon dioxide. The amine groups formed in situ by the isocyanate-water reaction can react with other free isocyanate groups to form urea crosslinks between the resin components. In this manner, the resin can be applied to a substrate, exposed to the ambient atmosphere, and cured to form a polyurethane coating on the substrate.

Summary of The Invention

Embodiments described herein relate to a moisture-curable, isocyanate-functional resin. The resin may comprise an aliphatic isocyanate functional material and a cycloaliphatic isocyanate functional material. The aliphatic isocyanate functional material may comprise the reaction product of an aliphatic diisocyanate and a hydroxy-functional ether compound. The cycloaliphatic isocyanate functional material may comprise the reaction product of a cycloaliphatic diisocyanate and a monofunctional alcohol compound. The resin is useful in formulating coating compositions that do not exhibit significant sag (sag) when applied at wet film thicknesses of at least 6 mils. The coating composition also exhibited no significant blistering (blistering) when cured to a dry film thickness of at least 6 mils.

Other embodiments disclosed herein relate to methods of increasing the sag resistance and blistering resistance of a coating composition. The method may include preparing a coating composition comprising a moisture-curable resin. The resin may comprise an aliphatic isocyanate functional material and a cycloaliphatic isocyanate functional material. The aliphatic isocyanate functional material may comprise the reaction product of an aliphatic polyisocyanate and a hydroxy-functional ether compound. The cycloaliphatic isocyanate functional material may comprise the reaction product of a cycloaliphatic polyisocyanate and a monofunctional alcohol compound. Coating compositions comprising the resin do not exhibit significant sag when applied at a wet film thickness of at least 6 mils. Coating compositions comprising the resin composition also exhibit no significant blistering when cured to a dry film thickness of at least 6 mils.

It is to be understood that the invention is not limited to the embodiments disclosed in the summary of the invention. It is intended that the present invention cover the modifications of this invention which fall within the scope of the invention, which is defined only by the claims.

Brief description of the drawings

Some of the features of the embodiments described can be better understood with reference to the accompanying drawings, in which:

FIG. 1 shows a gradient plate for measuring the film thickness to the applied coating composition;

FIG. 2 shows the percentage of initial gloss retained over 2000 hours of accelerated weathering for three (3) coating compositions and two (2) commercially available coating compositions prepared according to embodiments disclosed herein;

FIG. 3 is a bar graph of the percentage of initial gloss retained after 2000 hours of accelerated weathering for three (3) coating compositions and two (2) commercially available coating compositions prepared according to embodiments disclosed herein;

FIG. 4 is a bar graph of sag resistance (as evaluated by the wet film thickness without sag) and blistering resistance (as evaluated by the dry film thickness before blistering) for three (3) coating compositions and two (2) commercially available coating compositions prepared according to embodiments disclosed herein;

FIG. 5 shows the percentage of initial gloss that was retained within 2000 hours of accelerated weathering for ten (10) coating compositions prepared according to embodiments disclosed herein;

FIG. 6 is a bar graph of the percentage of initial gloss retained after 2000 hours of accelerated weathering for ten (10) coating compositions and two (2) commercially available coating compositions prepared according to embodiments disclosed herein;

FIG. 7 is a bar graph of sag resistance (as evaluated by the wet film thickness without sag) and blistering resistance (as evaluated by the dry film thickness before blistering) for ten (10) coating compositions and two (2) commercially available coating compositions prepared according to embodiments disclosed herein.

Detailed Description

It should be understood that some descriptions of the disclosed embodiments have been simplified to illustrate only elements, features, and aspects that are relevant for a clear understanding of the disclosed embodiments, while eliminating, for purposes of clarity, other elements, features, and aspects. One of ordinary skill in the art, upon considering the present description of the disclosed embodiments, will recognize that other elements and/or features may be desirable in a particular implementation or application of the disclosed embodiments. However, because such other elements and/or features may be readily ascertained by one of ordinary skill in the pertinent art based on consideration of the present description of the disclosed embodiments, they are not relevant for a complete understanding of the disclosed embodiments and a description of such elements and/or features is not provided herein. Accordingly, it is to be understood that the description set forth herein is merely exemplary of the disclosed embodiments and is not intended as a limitation on the scope of the invention, which is defined solely by the claims.

Unless otherwise indicated, all numbers expressing quantities or characteristics are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, any numerical parameters set forth in the following specification can vary depending upon the desired properties desired to be obtained in the compositions and methods of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter described herein should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Moreover, any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" includes all sub-ranges between (and including) the minimum value of 1 and the maximum value of 10, that is, all sub-ranges between equal to or greater than the minimum value (1) and equal to or less than the maximum value (10). Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited herein is intended to include all higher numerical limitations subsumed therein. Accordingly, applicants reserve the right to modify the disclosure (including the claims) to clearly state any sub-ranges subsumed within the ranges explicitly set forth herein. All of these ranges are themselves disclosed herein as being modified to clearly indicate that these sub-ranges comply with the requirements of 35u.s.c. § 112 first paragraph and 35u.s.c. § 132 (a).

As used herein, the modifiers "a", "an" and "the" are intended to include "at least one" or "one or more" unless the context clearly indicates otherwise. Thus, a modifier, as used herein, means one or more than one (i.e., at least one) of the subject(s) of the modifier. For example, "component" means one or more components, and thus, can be understood to mean more than one component, and more than one component can be utilized or used.

Any patent, publication, or other disclosure material, in whole or in part, that is said to be incorporated by reference herein is incorporated herein only to the extent that it is specifically recited in the following claims: that is, the material incorporated is not to be inconsistent with existing definitions, statements, or other disclosure material set forth herein. Thus, the disclosure herein necessarily supersedes any conflicting material incorporated herein by reference. Any material, or portion thereof, that is said to be incorporated by reference herein, but which conflicts with existing definitions, statements, or other disclosure material set forth herein is only incorporated to the extent that no conflict arises between that incorporated material and the existing disclosure material.

As used herein, the terms "film thickness" and "film thickness" are synonymous and refer to the depth (typically measured in mils, i.e., thousandths of an inch) of a coating composition applied to a substrate. Film thickness can be measured as wet film thickness ("WFT"), i.e., the depth of the coating composition applied to the substrate prior to curing. Film thickness can also be measured as dry film thickness ("DFT"), i.e., the depth to which a coating composition applied to a substrate has been cured. The WFT of the applied coating composition is typically measured shortly after the coating is applied. The DFT of an applied coating composition is generally measured after the coating composition is hard dried ("HD").

The term "aliphatic" as used herein refers to substituted or unsubstituted, straight-chain, branched-chain, and/or cyclic organic compounds composed of carbon atoms. Aliphatic compounds do not contain aromatic rings as part of the molecular structure of the compound. The term "alicyclic" as used herein refers to an organic compound in which carbon atoms are arranged in a closed ring structure. Alicyclic compounds do not contain an aromatic ring as part of the molecular structure of the compound. Thus, cycloaliphatic compounds are a subset of aliphatic compounds. Thus, the aliphatic composition may comprise aliphatic compounds and/or cycloaliphatic compounds.

The term "diisocyanate" as used herein refers to a compound containing two isocyanate groups. The term "polyisocyanate" as used herein refers to a compound containing two or more isocyanate groups. Thus, diisocyanates are a subset of polyisocyanates.

Coating compositions, such as isocyanate-based moisture-curable protective coatings, may require multiple applications when applied to a substrate due to coating film thickness limitations. For example, one limitation on the film thickness of an applied coating may be sag. Sag refers to the tendency of an applied liquid coating composition to move or spread over the surface of a substrate before it is cured. For example, when a liquid coating composition is applied to a vertically placed or tilted substrate, the liquid coating composition may move (i.e., sag) under the influence of gravity.

In general, the greater the WFT of an applied liquid coating composition, the greater the tendency of the applied coating composition to sag prior to curing. See astm d 4400-standard test method for sag resistance of paints obtained using a multi-notch applicator (standard test method for sagrististanscenes of paints using mulitnotchtester), which is incorporated herein by reference, for the purpose of illustrating the method of evaluating sag resistance. Sag in the applied liquid coating composition can adversely affect various coating properties, such as thickness uniformity and gloss of the cured coating. This may have a negative effect on the overall film thickness of the applied coating.

Another limitation on the film thickness of applied coatings, especially isocyanate-based moisture-curable coatings, is blistering. Blistering refers to the tendency of an applied moisture-curable coating composition to generate bubbles or craters. Isocyanate-based moisture-curable coatings can blister due to carbon dioxide gas being trapped under a portion of the at least partially cured coating film. Carbon dioxide gas is typically formed as the product of the isocyanate-water reaction, which occurs when isocyanate groups react with water to form amine groups, which in turn react with excess isocyanate groups to form urea groups. Isocyanate-based moisture-curable coatings prevent gas from escaping from the applied coating film, thereby forming gas-trapped pockets that appear as bubbles in the film. The trapped gas pressure may also exceed the strength of the partially cured film, penetrating the surface of the applied film, thereby forming voids or pits in the surface of the applied coating.

In general, the greater the thickness of the applied liquid coating, the greater the tendency of the applied coating to foam during cure. See astm d 714-standard test method for evaluating paint blistering (standard test method for evaluating blistering of paints), which is incorporated herein by reference, for an illustration of the method for evaluating blistering resistance. The occurrence of blistering of the applied coating composition may adversely affect various coating properties, such as thickness uniformity, gloss and weatherability of the cured coating. This may have a negative effect on the overall film thickness of the applied coating.

As a result, isocyanate-based moisture-curable coatings have previously been limited to applied WFTs of about 4-6 mils and cured DFTs of about 3-4 mils. When existing isocyanate-based moisture-curable coatings are applied at greater than 4-6 mil WFT, significant sag can occur in the applied coating, particularly when the coating is applied to a vertically-placed or tilted substrate. When existing isocyanate-based moisture-curable coatings are applied and cured to greater than a 3-4 mil DFT, significant blistering occurs in the cured coating.

Embodiments disclosed herein relate to isocyanate-based engineering resins having improved film-forming and coating properties compared to existing isocyanate-based resins. The engineering resins disclosed are aliphatic isocyanate functional materials. The engineered resin is useful in formulating moisture curable coating compositions that can be applied to a substrate at a WFT of greater than 6 mils and without significant sag. The disclosed engineering resins are useful in formulating moisture curable coating compositions that can be applied to a substrate and cured to a DFT of greater than 6 mils without significant blistering.

The expression "no apparent sagging" as used herein means a property of the applied liquid coating material that is not visibly sagging when evaluated according to astm d 4400. The expression "no significant blistering" as used herein means the property of the applied and cured liquid coating resulting in a cured film without observable moisture-cure blisters, as shown in fig. 1 and described below.

Moisture-curable coating compositions formulated with the disclosed engineering resins have better weatherability than coating compositions formulated with existing isocyanate-based resins. The improvement in weatherability can be evaluated according to astm d4587 (standard practice for fluorescent uv-condensation exposure of paints and related coatings) and/or astm d1014 (standard practice for conductive outdoor exposure testing of paints and coatings on metal substrates).

The disclosed engineering resins may comprise a combination of aliphatic isocyanate functional materials and cycloaliphatic isocyanate functional materials. The aliphatic isocyanate functional material may comprise the reaction product of an aliphatic diisocyanate and a hydroxy-functional ether compound. The cycloaliphatic isocyanate functional material may comprise the reaction product of a cycloaliphatic diisocyanate and a monofunctional alcohol compound. The aliphatic isocyanate functional material and the cycloaliphatic isocyanate functional material may each comprise at least one functional group selected from the group consisting of: isocyanurates, iminooxadiazines, uretdiones (uretdiones), allophanates, biurets, and any combinations thereof. The aliphatic and cycloaliphatic isocyanate functional materials may be prepared from and/or comprise polyisocyanates having an isocyanate functionality greater than 2.

Isocyanurates may be prepared by the cyclotrimerization of polyisocyanates. The trimerization reaction can be carried out, for example, by reacting three (3) equivalents of polyisocyanate to produce 1 equivalent of isocyanurate ring. The three (3) equivalent weight polyisocyanate may comprise three (3) equivalent weights of the same polyisocyanate compound, or various mixtures of two (2) or three different polyisocyanate compounds. Compounds such as phosphines, Mannich bases and tertiary amines such as 1, 4-diaza-bicyclo [2.2.2] octane, dialkylpiperazine and the like may be used as trimerization catalysts. Iminooxadiazines may be prepared by asymmetric cyclotrimerization of polyisocyanates. Uretdiones can be prepared by dimerization of polyisocyanates. Allophanates can be prepared by reacting polyisocyanates with urethanes. Biurets can be prepared by adding a small amount of water to two equivalents of polyisocyanate and reacting at slightly elevated temperatures in the presence of a biuretizing catalyst. Biurets can also be prepared by reacting polyisocyanates with urea.

Polyisocyanates useful in the production of isocyanurates, iminooxadiazines, biurets, uretdiones, and allophanates and in the production of aliphatic and cycloaliphatic isocyanate functional materials used in the engineering resins disclosed herein may include aliphatic and cycloaliphatic diisocyanates, such as 1, 2-ethanediisocyanate; 1, 4-tetramethylene diisocyanate; 1, 6-hexamethylene diisocyanate ("HDI"); 2, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate; 1, 12-dodecane diisocyanate; 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethyl-cyclohexane (isophorone diisocyanate or "IPDI"); two (a)4-isocyanatocyclohexyl) methane ('H')₁₂MDl "); bis- (4-isocyanato-3-methyl-cyclohexyl) methane, and any combination thereof. Other polyisocyanates, including various diisocyanates, that are also useful in the production of aliphatic and cycloaliphatic isocyanate functional materials may include the polyisocyanates disclosed in U.S. patent nos. 4,810,820, 5,208,334, 5,124,427, 5,235,018, 5,444,146 and 7,038,003, all of which are incorporated herein by reference. Any combination of the above definitions and the incorporated polyisocyanates may also be used to produce the aliphatic and cycloaliphatic isocyanate functional materials used in the disclosed engineering resins.

In various embodiments, isocyanate functional materials comprising adducts of polyisocyanates and hydroxyl functional compounds may be used in the disclosed engineering resins. For example, the isocyanate functional material may be formed by reacting an aliphatic or cycloaliphatic polyisocyanate with a hydroxy functional compound such as a monofunctional alcohol ("monol" or "monol"), a polyfunctional alcohol ("polyol"), a mixture of monols, a mixture of polyols, or a mixture of monols and polyols. For example, the polyisocyanate may be reacted with a hydroxyl functional compound to produce a polyisocyanate-hydroxyl compound adduct containing urethane and/or allophanate groups. In some embodiments, the polyisocyanate and the hydroxy-functional compound may be reacted at an OH to NCO molar ratio of 1: 1.5 to 1: 20. In other embodiments, the polyisocyanate and the hydroxy-functional compound may be reacted at an OH to NCO molar ratio of 1: 2 to 1: 15 or 1: 5 to 1: 15.

Polyisocyanates useful in the production of aliphatic and cycloaliphatic isocyanate functional materials may include, for example, the aliphatic and cycloaliphatic diisocyanates described above. Polyisocyanates useful in the production of isocyanate functional materials may also include, for example, compounds produced from the above diisocyanates comprising at least one functional group selected from the group consisting of: isocyanurates, iminooxadiazines, uretdiones, allophanates, biurets, and any combinations thereof.

Hydroxy-functional compounds useful in the production of aliphatic and cycloaliphatic isocyanate-functional materials may include, for example, low molecular weight mono-or polyhydric aliphatic alcohols (which may optionally contain ether groups), mono-or polyhydric cycloaliphatic alcohols (which may optionally contain ether groups), polythioethers, polyacetals, polycarbonates, polyesters, polyethers, and any combination thereof. Hydroxy-functional compounds useful in the production of aliphatic and cycloaliphatic isocyanate-functional materials may also include, for example, the hydroxy-containing compounds described in U.S. patent nos. 4,810,820, 5,208,334, 5,124,427, 5,235,018, 5,444,146, and 7,038,003, which are all incorporated herein by reference.

In various embodiments, hydroxyl functional polymeric and/or oligomeric polyethers can be used to produce the aliphatic isocyanate functional materials that comprise the disclosed engineering resins. The term "polyether" as used herein refers to ether group-containing polymeric and oligomeric compounds. Polyethers useful in the production of aliphatic isocyanate functional materials may include polyethers having 1 to 4 free hydroxyl groups. For example, polyethers can be prepared by oligomerization or polymerization of epoxides. These epoxides may include, for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin. The various epoxides can be reacted with the starting components having active hydrogen atoms, either individually (for example, in the presence of boron trifluoride) or as a mixture, or by adding the epoxide continuously to the starting components having active hydrogen atoms. Starting components useful in preparing the polyethers can include, for example, water, alcohols, and phenols. Suitable starting components may include, for example, ethylene glycol; (1, 3) -and (1, 2) -propylene glycol; and trimethylolpropane.

In various embodiments, the disclosed engineering resins comprise an aliphatic isocyanate functional material comprising the reaction product of a diisocyanate and a hydroxyl functional polyether. Hydroxy-functional polyethers that can be used to produce aliphatic isocyanate-functional materials can include, for example, hydroxy-functional alkylene ether polyols such as hydroxy-functional poly (tetramethylene glycol), poly (propylene oxide), poly (ethylene oxide) and poly (ethylene oxide-co-propylene oxide). Polyether polyols useful in the production of aliphatic isocyanate functional materials may also include, for example, ethylene oxide and/or propylene oxide adducts of polyols, such as ethylene oxide and/or propylene oxide adducts of ethylene glycol or butylene glycol. In some embodiments, polycaprolactone that functions similarly to hydroxyl-functional polyethers can be used to produce aliphatic isocyanate-functional materials that comprise the disclosed engineering resins.

In various embodiments, the hydroxyl functional compounds useful in the production of the cycloaliphatic isocyanate functional material can include, for example, one or more monofunctional alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol isomer, pentanol isomer, hexanol isomer, heptanol isomer, octanol isomer, nonanol isomer, decanol isomer, 2-ethylhexanol, trimethylhexanol, cyclohexanol, aliphatic alcohols having from 11 to 20 carbon atoms, vinyl alcohol, allyl alcohol, and any combination thereof. In some embodiments, monofunctional alcohols useful in the production of cycloaliphatic isocyanate functional materials may include straight chain, branched chain, or cyclic alcohols containing from 6 to 9 carbon atoms. In some embodiments, the monofunctional alcohol may comprise an ether group.

For example, the engineering resin may be prepared by: the aliphatic isocyanate functional material and the cycloaliphatic isocyanate functional material are mixed in a designed weight ratio that results in a coating composition that does not exhibit significant sag when applied at a wet film thickness of at least 6 mils. For example, engineering resins can also be prepared by: the aliphatic isocyanate functional material and the cycloaliphatic isocyanate functional material are mixed in a designed weight ratio that results in a coating composition that does not exhibit significant blistering when cured to a dry film thickness of at least 6 mils. For example, engineering resins can also be prepared by: the aliphatic isocyanate functional material and the cycloaliphatic isocyanate functional material are mixed in a designed weight ratio that results in a coating composition having better weatherability than existing isocyanate-based moisture-curable coating compositions.

For example, the engineering resin may be prepared by: the aliphatic isocyanate functional material and the cycloaliphatic isocyanate functional material are mixed in a weight ratio designed to produce a coating composition that exhibits no significant sag when applied at a WFT of 6 mils, 7 mils, 8 mils, 9 mils, 10 mils, 11 mils, 12 mils or greater. For example, engineering resins can also be prepared by: the aliphatic isocyanate functional material and the cycloaliphatic isocyanate functional material are mixed in a weight ratio designed to produce a coating composition that exhibits no significant blistering when cured to a DFT of 6 mils, 7 mils, 8 mils, 9 mils, 10 mils, 11 mils, 12 mils or greater. The engineering resin may be prepared by: the isocyanate functional materials are mixed in a designed weight ratio that results in a coating composition having any combination of the above properties.

In some embodiments, the aliphatic isocyanate functional material may comprise an HDI-based aliphatic isocyanate functional material. For example, the HDI-based aliphatic isocyanate-functional material may comprise at least one allophanate group. The HDI-based aliphatic isocyanate functional material may comprise, for example, the reaction product of a hydroxy-functional ether compound and HDI. For example, the ether compound may comprise a hydroxy-functional polyether. The hydroxyl functional polyether may comprise a polyether polyol such as described in U.S. patent No. 7,038,003, which is incorporated herein by reference.

In various embodiments, the hydroxyl-functional polyether has a number average molecular weight (M)_n) 300-. In some embodiments, the hydroxyl functional polyether has a number average molecular weight (M)_n) Is 1000-12000 g/mol, and in other embodiments is 1000-4000 g/mol.

Additionally, the hydroxyl-functional polyether may contain less than or equal to 0.02 milliequivalents of unsaturated end groups per gram of polyol (milliequivalents/gram), in some embodiments less than or equal to 0.015 milliequivalents/gram, and in other embodiments less than or equal to 0.01 milliequivalents/gram (determined in accordance with astm d2849-69, incorporated herein by reference). In addition, the hydroxy-functional polyethers have a relatively narrow molecular weight distribution (e.g.polydispersity (M)_w/M_n) 1.0 to 1.5) and/or an OH functionality of > 1.9. In some casesIn embodiments, for example, the hydroxyl functional polyether has an OH functionality of less than 6, or less than 4.

Hydroxy-functional polyethers useful in the disclosed engineering resins can be prepared by, for example, alkoxylating a suitable starter molecule using a double metal cyanide catalyst (DMC catalysis), as described in U.S. Pat. No. 5,158,922 and European patent application publication No. A0654302, which are incorporated herein by reference.

In various embodiments, the HDI-based aliphatic isocyanate-functional material may be prepared by reacting HDI with a polyether prepared using DMC catalysis. In some embodiments, the HDI-based aliphatic isocyanate-functional material comprises the reaction product of HDI and polypropylene glycol characterized in that the reaction product comprises allophanate groups.

The HDI-based aliphatic isocyanate-functional material may have an average isocyanate functionality of at least 4, a glass transition temperature of less than-40 ℃, and/or an% NCO of less than 10%. The HDI-based aliphatic isocyanate-functional material is substantially free of HDI isocyanurate trimer.

Aliphatic isocyanate-functional materials based on HDI comprise the reaction product of a hydroxyl-functional compound and HDI, having at least one allophanate group, and can be prepared according to the method described, for example, in U.S. patent No. 7,038,003.

In some embodiments, the cycloaliphatic isocyanate functional material may comprise an IPDI-based cycloaliphatic isocyanate functional material. For example, an IPDI-based cycloaliphatic isocyanate-functional material may comprise at least one allophanate group and at least one isocyanurate trimer group. The IPDI-based cycloaliphatic isocyanate functional material may comprise, for example, the reaction product of a monofunctional alcohol with IPDI. Monofunctional alcohols may include, for example, the monoalcohols described in U.S. Pat. Nos. 5,124,427, 5,235,018, 5,208,334, and 5,444,146, which are incorporated herein by reference.

In various embodiments, the IPDI-based cycloaliphatic isocyanate-functional material may be prepared by reacting IPDI with a monoalcohol to produce a polyisocyanate mixture having an NCO content of 10-47% by weight, a viscosity of less than 10,000mPa.s, containing isocyanurate and allophanate groups, wherein the molar ratio of monoisocyanurate to monoallophanate is 10: 1 to 1: 5. In some embodiments, the IPDI-based cycloaliphatic isocyanate functional material comprises the reaction product of IPDI and a monol selected from the group consisting of: methanol, ethanol, n-propanol, isopropanol, butanol isomers, pentanol isomers, hexanol isomers, heptanol isomers, octanol isomers, nonanol isomers, decanol isomers, 2-ethylhexanol, trimethylhexanol, cyclohexanol, fatty alcohols having from 11 to 20 carbon atoms, vinyl alcohol, allyl alcohol, and any combination thereof. In other embodiments, the monol may be selected from the group consisting of: methanol, ethanol, 1-butanol, 2-butanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, isocetyl alcohol, 1-dodecanol, and monohydroxypoly (ethylene oxide), characterized in that the IPDI reaction product contains isocyanurate and allophanate groups, wherein the molar ratio of monoisocyanurate to monoallophanate is from 10: 1 to 1: 5.

The cycloaliphatic isocyanate functional material based on IPDI has an average isocyanate functionality of at least 2.3, a glass transition temperature of between 25 ℃ and 65 ℃ and/or an% NCO of 10-47% by weight.

In various embodiments, the cycloaliphatic isocyanate functional material (e.g., IPDI-based cycloaliphatic isocyanate functional material) and the aliphatic isocyanate functional material (e.g., HDI-based aliphatic isocyanate functional material) may be combined in a weight ratio of from 1: 99 to 99: 1 (cycloaliphatic isocyanate functional material: aliphatic isocyanate functional material). In some embodiments, the engineering resin comprises a weight ratio of cycloaliphatic isocyanate functional material to aliphatic isocyanate functional material of from 95:5 to 50: 50. In some other embodiments, the engineering resin comprises a weight ratio of cycloaliphatic isocyanate functional material to aliphatic isocyanate functional material of from 75: 25 to 65: 35. In some other embodiments, the engineering resin comprises a weight ratio of cycloaliphatic isocyanate functional material to aliphatic isocyanate functional material of from 73: 27 to 69: 31.

In some embodiments, the engineering resin may comprise 50 to 100 wt% of a cycloaliphatic isocyanate functional material (e.g., IPDI based cycloaliphatic isocyanate functional material). The disclosed resins can include 0-50 wt.% of an aliphatic isocyanate functional material (e.g., an HDI-based aliphatic isocyanate functional material). In some other embodiments, the disclosed resins may comprise 50 wt% to 99 wt%, 50 wt% to 95 wt%, 50 wt% to 90 wt%, 50 wt% to 80 wt%, 50 wt% to 70 wt%, or 50 wt% to 60 wt% of the cycloaliphatic isocyanate functional material. In some other embodiments, the disclosed resins may comprise 1 wt% to 50 wt%, 5 wt% to 50 wt%, 10 wt% to 50 wt%, 20 wt% to 50 wt%, 30 wt% to 50 wt%, or 40 wt% to 50 wt% of the aliphatic isocyanate functional material.

In some embodiments, the disclosed resins may comprise 60 wt% to 99 wt%, 60 wt% to 95 wt%, 60 wt% to 90 wt%, 60 wt% to 80 wt%, or 60 wt% to 70 wt% of the cycloaliphatic isocyanate functional material. In some other embodiments, the disclosed resins may comprise 70 wt% to 99 wt%, 70 wt% to 95 wt%, 70 wt% to 90 wt%, or 70 wt% to 80 wt% of the cycloaliphatic isocyanate functional material. In some other embodiments, the disclosed resins may comprise 65 wt% to 75 wt% of cycloaliphatic isocyanate functional material.

In some embodiments, the disclosed resins may comprise 1 wt% to 40 wt%, 5 wt% to 40 wt%, 10 wt% to 40 wt%, 20 wt% to 40 wt%, or 30 wt% to 40 wt% of the aliphatic isocyanate functional material. In some other embodiments, the disclosed resins may comprise 1 wt% to 30 wt%, 5 wt% to 30 wt%, 10 wt% to 30 wt%, or 20 wt% to 30 wt% of the aliphatic isocyanate functional material. In some other embodiments, the disclosed resins may comprise 25 wt.% to 35 wt.% of the aliphatic isocyanate functional material.

The engineering resins have improved film forming and coating properties compared to existing isocyanate-based resin formulations. For example, the engineering resins may be used to formulate moisture curable coating compositions that can be applied with a WFT equal to or greater than 6 mils without significant sag (according to astm d 4400). The engineering resins are useful in formulating moisture curable coating compositions that can be applied and cured to a DFT of 6 mils or greater without significant blistering.

The blister resistance can be quantitatively analyzed by measuring the film thickness ("FBTB") of a coating composition comprising an isocyanate-based moisture-curable resin prior to blistering. The FBTB of the coating composition is the maximum DFT of the cured coating that does not exhibit significant blistering on panels having coatings applied in a thickness gradient. Figure 1 shows a gradient plate of FBTB used to measure the applied coating. The coating composition is applied to the panel at a thickness ranging from thin to thick. For example, the coating composition may be applied at a constant thickness gradient such that the cured coating has a 2 mil DFT at one end of the panel and a 12 mil DFT at the other end. If the cured coating exhibits significant blistering at a 7 mil DFT, the FBTB is 6 mils, and it is believed that the coating exhibits no significant blistering when applied at a DFT of at least 6 mils.

The engineered resins may also be used to formulate moisture-curable coating compositions having improved weatherability compared to prior moisture-curable coating compositions containing isocyanate-based resins. For example, moisture-curable coating compositions comprising the engineering resin have greater gloss retention after accelerated weathering in accordance with astm d4587 than moisture-curable coating compositions containing existing isocyanate-based resins. Moisture-curable coating compositions comprising engineering resins have greater gloss retention after exposure to south florida according to astm d1014 than moisture-curable coating compositions containing existing isocyanate-based resins.

In various embodiments, engineering resins may be used to formulate moisture-curable coating compositions. The moisture-curable coating composition may include an engineering resin and other components. In various embodiments, the moisture-curable coating composition may comprise, for example, an engineering resin, an additive resin, a pigment, a tinting paste, a pigment wetting agent, a pigment dispersant, a light stabilizer, a uv absorber, a rheology modifier, a defoamer, a dehydrating agent, a solvent, a catalyst, or an additive to affect, for example, substrate wetting, film leveling, coating surface tension, pigment abrasiveness, pigment deflocculation, or gloss.

In some embodiments, the moisture-curable coating composition may comprise an engineering resin and one or more additive resins, such as Joncryl611 (basf corporation) and/or neocryl b-734^TM(DSMN.V.)。Joncryl611 is a styrene-acrylic copolymer resin. Joncryl611 can be used as an additive resin in moisture curable coating compositions to affect, for example, pigment dispersibility and film formation. NeocrylB-734^TMIs methyl methacrylate, n-butyl methacrylate copolymer resin. NeocrylB-734^TMCan be used as an additive resin to affect, for example, pigment dispersibility and film-forming properties.

In some embodiments, the moisture-curable coating composition may include an engineering resin and one or more pigments, such as titanium dioxide. Pigments useful in the disclosed moisture-curable coating compositions can include, for example, Kronos^TM2310 (Comnonis International Inc. (Kronos Worldwide, Inc.)) and/or Ti-PureR-706 (DuPont). In some embodiments, the disclosed moisture-curable coating compositions may include one or more fillers. Fillers useful in the disclosed moisture-curable coating compositions can include, for example, ImsilA-10 (Yonimine corporation) and/or Nytal3300(r.t. van der bilt company).

In some embodiments, the moisture-curable coating composition may include an engineering resin and one or more pigment wetting or dispersing agents. Pigment wetting agents and dispersants useful in the disclosed moisture-curable coating compositions can include, for example, Disperbyk110(BYK Chemicals (BYK-Chemie GmbH)), Disperbyk192(BYK Chemicals), and/or Anti-TerraU (BYK Chemicals).

The moisture-curable coating composition may include an engineering resin and one or more rheology modifiers. Rheology modifiers useful in the disclosed moisture-curable coating compositions can include, for example, Byk430，Byk431(BYK Chemicals), bentonite (Bentoniteclays), and/or castor oil derivatives. In some embodiments, a moisture-curable coating composition may include the disclosed engineering resin and one or more defoamers. Defoamers that may be used in the disclosed moisture-curable coating compositions may include, for example, Byk077(BYK Chemicals).

In some embodiments, the moisture-curable coating composition may include an engineering resin and one or more light stabilizers and/or ultraviolet absorbers. Light stabilizers useful in the disclosed moisture-curable coating compositions can include, for example, Tinuvin292 (Ciba)/BASF). UV absorbers useful in the disclosed moisture-curable coating compositions can include, for example, Tinuvin1130 (Ciba)/BASF). In some other embodiments, the moisture-curable coating composition may comprise an engineering resin and one or more dehydrating agents. Dehydrating agents useful in the disclosed moisture-curable coating compositions may include, for example, p-toluenesulfonyl isocyanate, isophorone diisocyanate, and/or 1, 6-hexamethylene diisocyanate.

In other embodiments, the moisture-curable coating composition may comprise an engineering resin and one or more catalysts, such as dibutyltin dilaurate or tertiary amines. Catalysts useful in the disclosed moisture-curable coating compositions can include, for example, DabcoT-12 (air products and Chemicals, Inc.) and/or 1, 4-diazabicyclo [2.2.2]]Octane.

The moisture-curable coating composition may include an engineering resin and one or more other additives. Other additives useful in the disclosed moisture-curable coating compositions can include, for example, Byk358 and/or Byk306(BYK chemical company).

In some embodiments, the moisture-curable coating composition may include an engineering resin and one or more solvents. Solvents useful in the disclosed moisture-curable coating compositions may include, for example, methyl-n-amyl ketone ("MAK"), Aromatic^TM100 (ExxonMobil chemical Co., Ltd.), Aromatic^TM150 (Exxon Mobil chemical Co.), xylene, methyl isobutyl ketone ("MIBK"), ethyl 3-ethoxypropionate (Eastman chemical Co., Ltd.)^TMEEP solvents, Eastman chemical company (Eastman chemical company)), and/or methyl ethyl ketone ("MEK").

In various embodiments, the present invention also relates to methods of using the engineering resins and moisture-curable coating compositions comprising the engineering resins. Embodiments may include methods of increasing the sag resistance, blistering resistance, and/or weatherability of a coating composition. The method includes preparing a coating composition by adding the disclosed engineering resin. The resin may comprise aliphatic isocyanate functional materials and cycloaliphatic isocyanate functional materials as described herein. The coating compositions prepared containing the resin did not exhibit significant sag when applied at a wet film thickness of at least 6 mils. Coating compositions comprising the resin are prepared without significant blistering when cured to a dry film thickness of at least 6 mils.

Other embodiments of the invention may include methods of coating a substrate. The method includes applying the coating composition at a WFT of at least 6 mils. The coating composition includes a resin containing an aliphatic isocyanate functional material and a cycloaliphatic isocyanate functional material. The applied coating composition did not have significant sag problems.

Other embodiments may include methods of coating a substrate. The method includes applying the coating composition such that the coating cures to a DFT of at least 6 mils. The coating composition includes a resin containing an aliphatic isocyanate functional material and a cycloaliphatic isocyanate functional material. The cured coating composition did not exhibit significant blistering.

The following illustrative and non-limiting examples are presented to further describe the embodiments disclosed herein and are not intended to limit the scope of the invention. Those skilled in the art will appreciate that variations of the embodiments may be made within the scope of the invention, which is limited only by the claims. All parts and percentages are by weight unless explicitly stated otherwise.

Examples

Example 1

An aliphatic moisture-curable coating composition is prepared according to one embodiment. The coating composition comprises an engineering resin. An engineering resin is formed from an isocyanate functional material. The isocyanate functional material contained 28% by weight of an aliphatic HDI-based isocyanate functional material ("HDI-based material") and 72% by weight of an IPDI-based cycloaliphatic isocyanate functional material ("IPDI-based material")).

The HDI-based material comprises an allophanate reaction product of HDI with a hydroxy-functional polyether prepared using DMC catalysis. HDI was reacted with a polyether using the method described in us patent No. 7,038,018. Based on the HDI material, an average isocyanate functionality of 4 or more, a glass transition temperature of less than-40 ℃ and a% NCO of less than 10% by weight. The HDI-based material is substantially free of HDI isocyanurate trimer.

The IPDI-based material comprises the allophanate-modified isocyanurate trimer reaction product of IPDI and a monoalcohol. The IPDI is reacted with the monoalcohol using the methods described in U.S. Pat. Nos. 5,124,427 and 5,235,018. The IPDI-based material has an average isocyanate functionality of at least 2.3, a glass transition temperature of between 25 ℃ and 65 ℃ and a% NCO of 10 to 45% by weight.

The moisture-curable coating composition includes the components listed in table 1 in approximate weight percentages listed in table 1.

TABLE 1

Preparing a moisture-curable, aliphatic coating composition by: the components listed in Table 1 (from Joncryl) were added to the milling vessel611 to Nytal3300). The resulting mixture was ground until fineness of 6 hegman (about 30 minutes) was obtained. To the resulting dispersion was added MEK and Eastman^TMAn EEP solvent. A portion of the dispersion containing the added MEK and EEP was used to perform karl fischer titration to determine the amount of water in the total dispersion. P-toluenesulfonyl isocyanate ("PTSI") was added based on the amount of water in the dispersion. The PTSI-added dispersion was allowed to stand for 30 minutes, purged with PTSI and water removed. After 30 minutes, the isocyanate functional material was added followed by DabcoT-12 catalyst. The coating composition was allowed to mix for an additional 10 minutes. The coating composition had the properties shown in table 2.

TABLE 2

Example 2

An aliphatic moisture-curable coating composition is prepared according to one embodiment. The coating composition comprises an isocyanate functional material comprising 100% IPDI based material and 0% HDI based material. The composition comprises the components listed in table 3 in approximate weight percentages listed in table 3.

TABLE 3

A moisture-curable, aliphatic coating composition was prepared according to the procedure described in example 1. The coating compositions had the properties shown in table 4.

TABLE 4

Example 3

An aliphatic moisture-curable coating composition is prepared according to one embodiment. The coating composition comprises an isocyanate functional material comprising 88% HDI based material and 12% IPDI based material. The composition comprises the components listed in table 5 in approximate weight percentages listed in table 5.

TABLE 5

A moisture-curable, aliphatic coating composition was prepared according to the procedure described in example 1. The coating compositions had the properties shown in table 6.

TABLE 6

Example 4

The sag resistance of the aliphatic moisture-curable coating compositions prepared according to examples 1-3 was determined and compared to the sag resistance of two (2) commercially available polyester-modified aliphatic acrylic polyurethane formulated industrial coating compositions. Sag resistance was evaluated according to astm d4400 (standard test method for sag resistance of paints obtained using a multi-cut applicator (standarddtest method for satrististansceof paint using multinotch applicator)). The values determined for dry-to-touch (STT), hard-dry (HD), and sag resistance (maximum WFT without significant sag) are shown in table 7.

TABLE 7

Example 5

The blister resistance of aliphatic moisture-curable coating compositions prepared according to examples 1-3 was determined and compared to the blister resistance of two (2) commercial polyester-modified aliphatic acrylic polyurethane formulated industrial coating compositions. The blistering resistance was evaluated using the gradient plate described above. The values determined for dry-to-touch (STT), Hard Dry (HD), and blister resistance (FBTB/DFT, mils) are shown in table 8.

TABLE 8

Example 6

The weatherability of the aliphatic moisture-curable coating compositions prepared according to examples 1-3 was determined and compared to the weatherability of two (2) commercial polyester-modified aliphatic acrylic polyurethane formulated industrial coating compositions. Weather resistance was evaluated using the accelerated weathering method in accordance with astm d4587 (standard test procedure for fluorescent uv-condensation exposure of paints and related coatings (standard practice for fluorescent uv-condensation exposure of paintand related coatings)). According to ASTM

G154 (Standard practice for operating fluorescent devices for non-metallic UV Exposure) accelerated weathering in a QUV fluorescent UV/condensing device. The weatherability was quantified as the percent retention of initial gloss measured at a 60 degree angle. The results of the weather resistance evaluation are shown in fig. 2. The coating compositions prepared according to examples 1 and 2 and commercial coating composition 1 were subjected to accelerated weathering for 2000 hours. The coating composition prepared according to example 3 was subjected to accelerated weathering for 1500 hours and commercial coating composition 2 was subjected to accelerated weathering for 1966 hours.

Example 7

The coating compositions prepared according to examples 1-3 were compared to two (2) commercial coating compositions for sag resistance, blistering resistance, and weatherability. FIG. 3 is a bar graph comparing the percentage of initial gloss retained after 2000 hours of accelerated weathering according to example 6 (1500 hours of accelerated weathering for coating compositions prepared according to example 3, 1966 hours for commercial coating composition 2). The coating composition prepared according to example 1 (28% HDI-based material and 72% IPDI-based material) had the greatest percentage of initial gloss retention after accelerated weathering. This indicates improved weatherability compared to the two (2) commercially available coating compositions.

FIG. 4 is a bar graph comparing sag resistance values (maximum WFT without significant sag) and blister resistance values (FBTB/DFT) for each coating composition evaluated according to examples 4 and 5. Three (3) coating compositions prepared according to the disclosed embodiments outperform commercial coating compositions in both sag resistance and blister resistance. The coating composition prepared according to example 1 had sag and blister resistance that was more than twice the sag and blister resistance of the commercially available coating composition. Thus, coating compositions prepared according to various embodiments can be applied to a substrate at a thickness of at least 2 times or more without significant sagging or blistering and with enhanced weatherability compared to existing coating compositions.

Example 8

An aliphatic moisture-curable coating composition was prepared in accordance with ten (10) embodiments. The coating composition comprises an isocyanate functional material comprising an aliphatic isocyanate functional material based on HDI and a cycloaliphatic isocyanate functional material based on IPDI. Ten (10) coating compositions each contained the engineering resin shown in table 9.

TABLE 9

The coating compositions contained the components listed in table 10, which are approximate weight percentages listed in table 10.

Watch 10

A coating composition is prepared by: the components listed in Table 10 (from Joncryl) were added to the milling vessel611 to Nytal3300, including Nytal3300). The resulting mixture was ground until fineness of 6 hegman (about 30 minutes) was obtained. To the resulting pigment grind was added MEK and Eastman^TMAn EEP solvent. A portion of the pigment grind containing the added MEK and EEP was used to perform karl fischer titration to determine the amount of residual water in the total pigment grind. PTSI was added based on the amount of water in the pigment grind. The pigment grind with the PTSI added is allowed to stand for 30 minutes, cleaned with PTSI and reacted to remove residual water. After 30 minutes, the isocyanate functional material was added followed by DabcoT-12 catalyst. The coating composition was allowed to mix for an additional 10 minutes. The coating compositions had the properties shown in table 11.

TABLE 11

Example 9

The sag resistance and blister resistance of the aliphatic moisture-curable coating composition prepared according to example 8 were determined and compared to the sag resistance and blister resistance of two (2) commercial polyester-modified aliphatic acrylic polyurethane formulated industrial coating compositions. Sag resistance was evaluated according to astm d4400 (standard test method for sag resistance of paints obtained using a multi-cut applicator (standarddtest method for satrististansceof paint using multinotch applicator)). The blistering resistance was evaluated using the gradient plate described above. The values determined for sag resistance (WFT, mil) and blister resistance (FBTB/DFT, mil) are shown in table 12.

TABLE 12

Coating composition	Sagging	Foaming
			A	5.5	10.5
B	5.5	10.6
			C	5.0	11.2
D	6.0	9.7
			E	6.5	11.2
F	6.5	5.6
			G	8.0	4.7
H	9.0	4.9
			I	10.0	4.6
J	12.0	4.7
			Commercial purchase of-1	4.0	2.3
Commercial purchase of-2	4.0	3.1

Example 10

The weather resistance of the moisture-curable aliphatic coating compositions prepared according to example 8 was evaluated using the accelerated weathering method in accordance with astm d4587 (standard test procedure for fluorescent uv-condensation exposure of paints and related coatings). Accelerated weathering was performed in a QUV fluorescent UV/condensing unit according to ASTMG154 (Standard practice for operating fluorescent devices for non-metallic UV Exposure materials). Weatherability is quantified as the percent retention of initial gloss measured at a 60 degree angle. The results of the weather resistance evaluation are shown in fig. 5. The coating composition prepared according to example 8 was subjected to accelerated weathering for 2000 hours.

Example 11

The coating composition prepared according to example 8 was compared to two (2) commercially available coating compositions for sag resistance, blistering resistance, and weatherability. FIG. 6 is a bar graph comparing the percentage of initial gloss retained after 2000 hours of accelerated weathering according to example 10 (1966 hours of accelerated weathering for commercial coating composition 2). A coating composition prepared according to example 8 included the engineering resin of the disclosed embodiment and included 50%, 60%, 70%, 80%, 90%, and 100% IPDI-based material (50%, 40%, 30%, 20%, 10%, and 0% HDI-based material, respectively). The coating composition prepared according to example 8 has enhanced weatherability compared to at least one of the two (2) commercially available coating compositions.

FIG. 7 is a bar graph comparing sag resistance values (WFT) and blistering resistance values (FBTB/DFT) for each coating composition evaluated according to example 9. Ten (10) coating compositions (a-J) prepared according to the disclosed embodiments exceed commercially available coating compositions in both sag resistance and blistering resistance. The coating compositions a-F have a blister resistance that is more than twice as good as at least one of the commercially available coating compositions. Thus, coating compositions prepared according to various embodiments can be applied to a substrate and cured to a DFT of at least 2 times or more thickness without significant blistering and with enhanced weatherability compared to existing coating compositions.

Example 12

An aliphatic moisture-curable coating composition is prepared according to one embodiment. The coating composition comprises an isocyanate functional material comprising 27.3% HDI based material and 72.7% IPDI based material. The composition comprises the components listed in table 13 in approximate weight percentages listed in table 13.

Watch 13

A coating composition is prepared by: the components listed in Table 13 (from Joncryl) were added to the milling vessel611 to Nytal3300, including Nytal3300). The resulting mixture was ground until fineness of 6 hegman (about 30 minutes) was obtained. To the resulting pigment grind was added MAK and Eastman^TMAn EEP solvent. A portion of the pigment grind containing the added MAK and EEP was used to perform karl fischer titration to determine the amount of residual water in the total pigment grind. The entire pigment grind was heated to 150 ° f under vacuum of-90 kPa and held for 2 hours. The pigment grind was allowed to cool to room temperature under vacuum. The vacuum was stopped. Some more MAK was added in an amount equal to the mass of solvent evaporated from the pigment grind under vacuum.

A portion of the pigment grind with additional MAK added was used to perform karl fischer titration to determine the amount of residual water in the total pigment grind. PTSI was added based on the amount of residual water in the pigment grind. The pigment grind with the PTSI added is allowed to stand for 30 minutes, cleaned with PTSI and reacted to remove residual water. After 30 minutes, the engineering resins (IPDI allophanate and HDI polyether) were added) Then add DabcoT-12 and 1, 4-diazabicyclo [2.2.2]-octane. The coating composition was placed under vacuum of-90 kPa for an additional 30 minutes at room temperature. The coating compositions had the properties shown in table 14.

TABLE 14

Example 13

The sag resistance, blister resistance and weatherability of the aliphatic moisture-curable coating composition prepared according to example 12 were determined and compared to the sag resistance and blister resistance of commercial polyester-modified aliphatic acrylic polyurethane formulated industrial coating compositions. Sag resistance was evaluated according to astm d4400 (standard test method for sag resistance of paints obtained using a multi-cut applicator (standarddtest method for satrististansceof paint using multinotch applicator)). The blistering resistance was evaluated using the gradient plate described above. Four (4) different test conditions were evaluated in the blistering resistance test: (1) film thickness before foaming (DFT, mil) cured on a flat-laid substrate at 72 ° f and 50% relative humidity ("fbtb (h) -72/50"); (2) film thickness before foaming (DFT, mil) on a vertically positioned substrate cured at 72 ° f and 50% relative humidity ("fbtb (v) -72/50"); (3) film thickness before foaming (DFT, mil) cured on a flat-laid substrate at 95 ° f and 90% relative humidity ("fbtb (h) -95/90"); and (4) film thickness before foaming (DFT, mil) cured on a vertically positioned substrate at 95 ° f and 90% relative humidity ("fbtb (v) -95/90").

Weather resistance was evaluated using the accelerated weathering method in accordance with astm d4587 (standard test procedure for fluorescent uv-condensation exposure of paints and related coatings (standard practice for fluorescent uv-condensation exposure of paintand related coatings)). Accelerated weathering was performed in a QUV fluorescent UV/condensing unit according to ASTMG154 (Standard practice for operating fluorescent devices for non-metallic UV Exposure materials). Weatherability is quantified as the percent retention of initial gloss measured at a 60 degree angle after 2000 hours of accelerated weathering. The evaluation results are shown in Table 15.

Watch 15

Example 14

The weatherability of the moisture-curable aliphatic coating composition prepared according to example 12 was evaluated according to astm d1014 (standard practice for painting of metal substrates and conducting outdoor exposure testing of coatings) (standard south florida weathering method). For comparison purposes, commercial coating compositions were also evaluated for south florida weatherability. The coating composition was applied to a vertically placed steel substrate at 12:00 pm. The air temperature was 93 ℃ F. and the relative humidity was 60%. The temperature of the steel substrate was 102 ° f and the temperature of the coating composition was 95 ° f. The coating compositions were also evaluated for sag resistance and blistering resistance under these conditions.

The weatherability was quantified as the percent hold of the initial gloss measured at a 60 degree angle in accordance with astm d523 (standard method of testing for specular gloss). The evaluation results are shown in Table 16.

TABLE 16

The invention has been described in terms of some exemplary illustrative and non-limiting embodiments. However, those of ordinary skill in the art will recognize that various substitutions, alterations, or combinations of any of the disclosed embodiments (or portions thereof) can be made without departing from the scope of the invention as defined by the claims. Accordingly, it is to be understood and appreciated that the invention includes other embodiments not explicitly described herein. These embodiments may be implemented, for example, by combining, modifying or recombining any of the disclosed steps, ingredients, components, parts, elements, features, aspects, etc. of the embodiments disclosed herein in any manner that is found feasible by one of ordinary skill in the art. Accordingly, the present invention is not limited by the illustrative embodiments, but only by the appended claims.

Claims (12)

1. A moisture-curable resin comprising:

an aliphatic isocyanate functional material comprising the allophanate reaction product of 1, 6-hexamethylene diisocyanate and a hydroxy-functional polyether having a number average molecular weight (M)_n) 300-; and

a cycloaliphatic isocyanate functional material comprising the allophanate-modified isocyanurate trimer reaction product of isophorone diisocyanate and a monofunctional alcohol;

wherein a coating composition comprising the resin does not significantly sag when applied at a wet film thickness of at least 6 mils, and the coating composition does not significantly blister when cured to a dry film thickness of at least 6 mils; and

the weight ratio of cycloaliphatic isocyanate functional material to aliphatic isocyanate functional material is 95:5 to 50: 50.

2. The resin of claim 1, wherein the aliphatic isocyanate-functional material comprises an allophanate reaction product of 1, 6-hexamethylene diisocyanate and a hydroxyl-functional polyether prepared using double metal cyanide catalysis.

3. The resin of claim 1, wherein the aliphatic isocyanate-functional material comprises an allophanate reaction product of 1, 6-hexamethylene diisocyanate and a hydroxy-functional ether compound, wherein the aliphatic isocyanate-functional material has an isocyanate functionality of at least 4, a glass transition temperature of less than-40 ℃, and a% NCO of less than 10% by weight.

4. The resin of claim 1, wherein the cycloaliphatic isocyanate functional material comprises an allophanate-modified isocyanurate trimer reaction product of isophorone diisocyanate and a monofunctional alcohol selected from the group consisting of: methanol, ethanol, n-propanol, isopropanol, butanol isomers, pentanol isomers, hexanol isomers, heptanol isomers, octanol isomers, nonanol isomers, decanol isomers, 2-ethylhexanol, trimethylhexanol, cyclohexanol, fatty alcohols having from 11 to 20 carbon atoms, vinyl alcohol, allyl alcohol, and any combination of these monofunctional alcohols.

5. The resin of claim 1, wherein the cycloaliphatic isocyanate functional material comprises the reaction product of isophorone diisocyanate and a monofunctional alcohol, the cycloaliphatic isocyanate functional material has an isocyanate functionality of at least 2.3 and a glass transition temperature of between 25 ℃ and 65 ℃.

6. A coating composition comprising the moisture-curable resin of claim 1.

7. A method of increasing sag resistance, blistering resistance, and weatherability of a coating composition, the method comprising:

preparing a coating composition comprising a moisture-curable resin comprising:

an aliphatic isocyanate functional material comprising the allophanate reaction product of 1, 6-hexamethylene diisocyanate and a hydroxy-functional polyether having a number average molecular weight (M)_n) 300-; and

a cycloaliphatic isocyanate functional material comprising the allophanate-modified isocyanurate trimer reaction product of isophorone diisocyanate and a monofunctional alcohol;

wherein a coating composition comprising the resin does not significantly sag when applied at a wet film thickness of at least 6 mils, and the coating composition does not significantly blister when cured to a dry film thickness of at least 6 mils;

the resin comprises a weight ratio of cycloaliphatic isocyanate functional material to aliphatic isocyanate functional material of from 95:5 to 50: 50.

8. The method of claim 7, wherein the aliphatic isocyanate functional material comprises an allophanate reaction product of 1, 6-hexamethylene diisocyanate and a hydroxyl functional polyether prepared using double metal cyanide catalysis.

9. The method of claim 7, wherein the aliphatic isocyanate functional material comprises an allophanate reaction product of 1, 6-hexamethylene diisocyanate and a hydroxy-functional ether compound, wherein the aliphatic isocyanate functional material has an isocyanate functionality of at least 4, a glass transition temperature of less than-40 ℃, and a% NCO of less than 10% by weight.

10. The method of claim 7, wherein the cycloaliphatic isocyanate functional material comprises an allophanate-modified isocyanurate trimer reaction product of isophorone diisocyanate and a monofunctional alcohol selected from the group consisting of: methanol, ethanol, n-propanol, isopropanol, butanol isomers, pentanol isomers, hexanol isomers, heptanol isomers, octanol isomers, nonanol isomers, decanol isomers, 2-ethylhexanol, trimethylhexanol, cyclohexanol, fatty alcohols having from 11 to 20 carbon atoms, vinyl alcohol, allyl alcohol, and any combination of these monofunctional alcohols.

11. The method of claim 7, wherein the cycloaliphatic isocyanate functional material comprises the reaction product of isophorone diisocyanate and a monofunctional alcohol, the cycloaliphatic isocyanate functional material has an isocyanate functionality of at least 2.3 and a glass transition temperature of between 25 ℃ and 65 ℃.

12. A moisture-curable resin consisting of:

an aliphatic isocyanate functional material comprising the allophanate reaction product of 1, 6-hexamethylene diisocyanate and a hydroxy-functional polyether having a number average molecular weight (M)_n) 300-;

a cycloaliphatic isocyanate functional material which is the reaction product of isophorone diisocyanate and an allophanate-modified isocyanurate trimer of a monofunctional alcohol; and

optionally other components selected from additive resins, pigments, dye pastes, pigment wetting agents, pigment dispersants, light stabilizers, uv absorbers, rheology modifiers, defoamers, dehydrating agents, solvents, catalysts;

wherein a coating composition comprising the resin does not significantly sag when applied at a wet film thickness of at least 6 mils, and the coating composition does not significantly blister when cured to a dry film thickness of at least 6 mils; and

the weight ratio of cycloaliphatic isocyanate functional material to aliphatic isocyanate functional material is 95:5 to 50: 50.