Patent Application
20200048494
The application of coatings to metals to retard or inhibit corrosion is well established. Polyurethane coatings are often used for corrosion protection of steel, as these coatings are economical and relatively easy to apply. The coatings dry quickly and have good impact resistance, making the coatings especially useful for coating steel components to be transported or shipped over large distances, for example. The use of polyurethane coatings on unprimed metal surfaces reduces the cost of material and machinery required to make metal substrates durable and resistant to corrosion.
Presently, however, most polyurethane systems directly applied to unprimed or un-pretreated metal surfaces show inconsistent adhesion on various substrates, and in the absence of primer or pretreatment, the metal surface tends to corrode and blister quickly in humid conditions. Coatings modified with epoxy resins to improve adhesion tend to degrade and lose color and gloss on exposure to sunlight.
From the foregoing, it will be appreciated that there is a need for polyurethane coating compositions that can be applied to metal substrates with good adhesion and optimal corrosion resistance, while maintaining color and gloss on prolonged exposure to sunlight.
This invention provides a urethane coating composition useful in a variety of applications such as, for example, as a direct-to-metal coating, i.e. a coating composition that can be applied directly to the surface of a metal substrate without a primer, or more preferably, without a pretreatment. The coating composition preferably includes a polyol that is the reaction product of a resin of general formula (I) with an acid or a diol, with the reaction being carried out in the presence of a catalyst. The coating composition also includes an isocyanate-functional compound as a crosslinker. The coating composition forms a corrosion-resistant film when applied directly to the substrate surface without a primer or pretreatment.
In an embodiment, the urethane coating composition includes a polyol that is the reaction product of a resin of general formula (I) and an acid or diol, with the reaction being carried out in the presence of a catalyst. The resin has the structure shown below as formula (I):
wherein:
wherein each R1 is independently H, unsubstituted C1-C4 alkyl, or C1-C4 alkyl substituted with —OH or C1-C4 alkoxy; and
The present description provides a urethane coating composition that includes the polyol described herein, and an isocyanate-functional compound used as a crosslinker. The coating composition is useful in coating a variety of substrates, preferably metal substrates. In preferred embodiments, the coating composition is useful as a corrosion-resistant direct-to-metal coating that can be applied over a wide variety of metal substrates without a primer or other pretreatment. In alternative embodiments, the coating composition may be applied as a corrosion-resistant or rust-proofing primer. The coating composition may also have utility in a variety of other coating end uses, including, for example, coatings for non-galvanized metal, wood, masonry, aluminum, machinery, motors, tools, toolboxes, transportation equipment, cabinets, steel bars and railings, pipelines, drums, conduit, ducts, furniture, marking hazard areas, color coding equipment, and the like.
In one embodiment, a method of coating a substrate is provided herein. The method includes: providing a metal substrate, and applying to at least a portion of the substrate a urethane coating composition that includes a polyol that is reaction product of a resin of general formula (I) with an acid or a diol, and an isocyanate-functional compound as a crosslinker. This is followed by curing the composition to provide a corrosion-resistant coating on the substrate surface. Typically, the substrate is a metal substrate, although the coating composition may be used to coat other substrate materials if desired.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list. Unless otherwise indicated, the structural representations included herein are not intended to indicate any particular stereochemistry and are intended to encompass all stereoisomers.
As used herein, the term “organic group” means a hydrocarbon group (with optional elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, and silicon) that is classified as an aliphatic group, a cyclic group, or combination of aliphatic and cyclic groups (e.g., alkaryl and aralkyl groups). The term “cyclic group” means a closed ring hydrocarbon group that is classified as an alicyclic group or an aromatic group, both of which can include heteroatoms. The term “alicyclic group” means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.
The term “aryl group” (e.g., an arylene group) refers to a closed aromatic ring or ring system such as phenylene, naphthylene, biphenylene, fluorenylene, and indenyl, as well as heteroarylene groups (i.e., a closed aromatic or aromatic-like ring hydrocarbon or ring system in which one or more of the atoms in the ring is an element other than carbon (e.g., nitrogen, oxygen, sulfur, etc.)). Suitable heteroaryl groups include furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, purinyl, quinazolinyl, pyrazinyl, 1-oxidopyridyl, pyridazinyl, triazinyl, tetrazinyl, oxadiazolyl, thiadiazolyl, and so on. When such groups are divalent, they are typically referred to as “arylene” or “heteroarylene” groups (e.g., furylene, pyridylene, etc.)
A group that may be the same or different is referred to as being “independently” something.
Substitution is anticipated on the organic groups of the compounds of the present invention. The term “group” is used to describe a chemical substituent, where the described chemical material includes the unsubstituted group and that group with O, N, Si, or S atoms, for example, in the chain (as in an alkoxy group) as well as carbonyl groups or other conventional substitution. For example, the phrase “alkyl group” is intended to include not only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like, but also alkyl substituents bearing further substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus, “alkyl group” includes ether groups, haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls, etc. As used herein, the term “group” is intended to be a recitation of both a particular moiety, as well as a recitation of the broader class of substituted and unsubstituted structures that includes the moiety.
The term “phenylene” as used herein refers to a six-carbon atom aryl ring (e.g., as in a benzene group) that can have any substituent groups (including, e.g., hydrogen atoms, halogens, hydrocarbon groups, oxygen atoms, hydroxyl groups, etc.). Thus, for example, the following aryl groups are each phenylene rings: —C6H4—, —C6H3(CH3)—, and —C6H(CH3)2Cl—.
The term “polyol” refers to a polymer with two or more hydroxyl (—OH) groups. As used herein, the term may refer to different types of polyols, including, for example, polyether polyols, polyester polyols, and the like.
The term “crosslinker” refers to a molecule capable of forming a covalent linkage between polymers or between two different regions of the same polymer.
As used herein, the term “direct-to-metal” (DTM) implies that a coating composition is applied directly to the surface of a metal substrate, where the substrate has not been previously coated with a primer, pretreatment or other coating. As used herein, the term “pretreatment” refers to any organic coating applied to a substrate surface prior to the application of a paint or other protective coating, but does not include standard procedures and/or substances used to clean or prepare the surface, such as, for example, blasting, phosphate-treating, and the like. Therefore, a DTM coating applied without pretreatment may be applied to a clean-blasted surface, a phosphate-treated surface, and the like. DTM coatings combine the adhesion and corrosion resistance of a traditional primer coating with the durability, weatherability and gloss of a topcoat composition. Unless otherwise indicated, a DTM coating does not require prior pretreatment or application of a primer, or the subsequent application of a topcoat.
The term “on,” when used in the context of a coating applied on a surface or substrate, includes both coatings applied directly or indirectly to the surface or substrate. Thus, for example, a coating applied to a primer layer overlying a substrate constitutes a coating applied on the substrate.
Unless otherwise indicated, the term “polymer” includes both homopolymers and copolymers (e.g., polymers of two or more different monomers). Similarly, unless otherwise indicated, the use of a term designating a polymer class such as, for example, “polyether” is intended to include both homopolymers and copolymers (e.g., polyether-ester copolymers).
The terms “comprises” and variations thereof do not have a limiting meaning where these terms appear in the description and claims.
The terms “preferred” and “preferably” refer to embodiments of the invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances.
Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
As used herein, “a,” “an,” “the,” “at least one,” and “one or more” are used interchangeably. Thus, for example, a coating composition that comprises “a” polyether can be interpreted to mean that the coating composition includes “one or more” polyethers.
Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). Furthermore, disclosure of a range includes disclosure of all subranges included within the broader range (e.g., 1 to 5 discloses 1 to 4, 1.5 to 4.5, 4 to 5, etc.).
In one aspect, the present invention provides a urethane coating composition that includes a polyol that is a reaction product of a resin of general formula (I) with an acid or a diol. The composition also includes an isocyanate-functional compound as a crosslinker, and provides a corrosion-resistant film when applied to a metal substrate. Although the ensuing discussion focuses primarily on direct-to-metal coatings, it is contemplated that the composition described herein, as well as variations thereof, may be applied as primers or topcoats, and on a variety of different substrates, and for a variety of other end uses.
Coating compositions described herein preferably include at least a film-forming amount of the urethane described herein, along with a crosslinker. In addition, the coating composition may also include one or more additional ingredients such as, for example, a liquid carrier, and any other optional additives. Suitable additives include pigments, dispersing agents, uv stabilizers, adhesion promoters, and the like.
Coating compositions of the present invention may have utility in a variety of coating end uses, preferably end uses that employ a metal substrate. Preferred coating compositions exhibit a superior combination of coating properties, including optimal adhesion to the substrate, flexibility, impact resistance, corrosion resistance, durability, uv resistance (i.e. the coatings maintain optimal color and/or gloss after significant exposure to uv radiation), and a blister-free appearance. It is also contemplated that the coating composition may have utility in coating applications where a single-phase coating, i.e. a direct-to-metal coating that can be used without a primer or pretreatment of the substrate, is desired.
In preferred embodiments, the polyol described herein, is derived from a resin of the general formula (I):
wherein:
wherein R1 and R2 are independently H, unsubstituted C1-C4 alkyl, or C1-C4 alkyl substituted with —OH or C1-C4 alkoxy;
In preferred embodiments, each R in general formula (I) is an epoxide group, wherein when one of R1 and R2 is independently —CH2—, the other is hydrogen.
In some embodiments, in the general formula (I), each A is independently a organic group, such as, for example, a hydrocarbon group having from 1 to 6 carbon atoms (C1-C6 alkyl, alkenyl, or aryl), —C(O)—, —O—, —S—, —S(O)—, or —S(O)2—. Although unsubstituted alkyl or aryl groups are preferred, each A is intended to include not only pure open chain saturated hydrocarbon alkyl groups, such as methyl, methylene, ethyl, propyl, t-butyl, and the like, but also alkyl substituents bearing further substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc. Similarly, where A is an aryl group, each A is intended to include not only unsubstituted arylene rings, but also arylene rings substituted with saturated alkyl groups, alkenyl groups or aralkyl groups bearing further substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, and the like. Each A may also include arylene rings substituted with other substituents known in the art, including, without limitation, halogen substituents (Cl, Br, I, and the like), —OR′O groups, wherein R′ is substituted or unsubstituted C1-C4 alkyl, or —OR groups, wherein each R is independently H, C1-C4 alkyl, or an epoxide group of the formula:
wherein R1 and R2 are independently H, unsubstituted C1-C4 alkyl, or C1-C4 alkyl substituted with —OH or C1-C4 alkoxy. In a preferred embodiment, each A in general formula (I) is a methylene group, —CH2—, when m in general formula (I) is 1, and a phenylene ring substituted with an OR′O group, wherein R′ is —CH2—CH(OH)—CH2—, when m in general formula (I) is 0.
In preferred embodiments, the group -Ph- in general formula (I) represents an aromatic ring, specifically a phenylene ring. In an aspect, the phenylene ring is unsubstituted at the carbon atoms not attached to the A or —O—R segments of general formula (I), i.e. Ph is a symbol representing a —C6H4— group. In another aspect, each Ph is independently a phenylene ring substituted with hydrogen, a saturated or unsaturated hydrocarbon group with 1 to 4 carbon atoms, more preferably a saturated hydrocarbon group that may optionally include one or more heteroatoms other than carbon or hydrogen atoms (e.g., N, O, S, Si, a halogen atom, etc.). Examples of suitable hydrocarbon groups may include substituted or unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, butyl groups, etc., including isomers thereof), alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, or combinations thereof. Suitable other substitutes on the phenylene ring in general formula (I) also include halogens such as Cl, Br, and the like, —OR′O, wherein R′ is unsubstituted or substituted C1-C4 alkyl, or —OR groups, wherein each R is independently H, C1-C4 alkyl, or an epoxide group of the formula:
wherein each R1 is independently H, unsubstituted C1-C4 alkyl, or C1-C4 alkyl substituted with —OH or C1-C4 alkoxy. In a preferred embodiment, each Ph in general formula (I) is independently an unsubstituted phenylene ring, or a phenylene ring substituted with hydrogen, or a phenylene ring substituted with —OR, wherein R is an epoxide group of the formula:
In the general formula (I), n is selected based on the desired molecular weight of the polyol described herein. In an aspect, the desired molecular weight (number average molecular weight, Mn) is dictated by the ultimate end use of the urethane coating composition. Typically, the desired molecular weight of the polyol is preferably between 400 and 6000, and more preferably 1000 to 3000. Accordingly, in the general formula (I), n is between 0 and 6, preferably 0.05 to 4, more preferably 0.5 to 3.
In a preferred embodiment, the polyol described herein is derived from a resin with the following structure (A) or (B):
The structure (A) represents a resin of the general structural formula (I) where R is an epoxide group with one of either R1 or R2 as —CH2— and the remaining R1 and R2 as H, each A is —CH2—, each Ph (i.e. each phenylene ring) is independently unsubstituted or substituted with an —OR group, wherein R is an epoxide group as shown, m is 1, and n is 1.6 to 3.5. The structure (B) represents a resin of the general structural formula (I), where each R is an epoxide group as defined above, each -Ph- is a phenylene ring substituted with a dimethylbenzyl group,—each A is a phenylene ring substituted with OR′O—, wherein R′ is —CH2—CH(OH)—CH2—, m is 0, and n is 0.05 to 0.1.
In an embodiment, the polyol described herein is the product of the reaction of a resin of the general formula (I) with an acid or diol. Suitable acids include aliphatic and aromatic monocarboxylic and dicarboxylic acids, saturated and/or unsaturated fatty acids, and the like. In an aspect, aliphatic acids used in the preparation of the polyol described herein include monocarboxylic acids, such as, for example, acetic acid, butanoic acid, hexanoic acid, acrylic acid, methacrylic acid, 2-ethyl hexanoic acid, cyanoacrylic acid, crotonic acid, dodecanoic acid, fatty acid dimers, and the like. In another aspect, aliphatic acids used in the preparation of the polyol described herein include dicarboxylic acids such as, for example, succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decane di-acid, dodecane di-acid, abietic acid, acid dimers, and the like. The aliphatic acids may be straight-chain or branched acids. In yet another aspect, aromatic acids used in the preparation of the polyol described herein include aromatic monocarboxylic acids, such as, without limitation, alkyl substituted aromatic acids, alkenyl substituted aromatic acids, or hydroxy substituted aromatic acids. Examples include benzoic acid, hydroxy benzoic acid, cinnamic acid, and the like. In another aspect, aromatic acids include dicarboxylic acids such as, for example, isophthalic acid, terephthalic acid, phthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid (CHDA), oxy dibenzoic acid and the like. In an embodiment, a monocarboxylic aromatic acid, preferably benzoic acid, is used.
Suitable diols used in the preparation of the polyol described herein include aliphatic diols selected from unsubstituted or alkyl-substituted aliphatic diols. Examples include, without limitation, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, trimethylol propane, glycerol, and the like. In an embodiment, an unsubstituted diol, preferably 1,4-butanediol, is used.
In an embodiment, the acid or diol is present in an amount sufficient to react substantially all the epoxide groups, if present, in general formula (I). In an aspect, the amount of acid or diol needed to react substantially all the epoxide groups depends on the value of n in general formula (I), i.e. larger amounts of the acid or diol may be required for larger values of n. In a preferred embodiment, where n is preferably between 0.05 and 3, the amount of acid or diol sufficient to react substantially all the epoxide groups in general formula (I) is preferably between about 1 to 4 moles, more preferably about 1.5 to 3.5 moles. As used herein, reacting substantially all the epoxide groups in the resin implies that the epoxy equivalent weight per 100 g of the polyol is about 0.0001 to 0.01.
In an embodiment, the polyol described herein is the product of a reaction between a compound of general formula (I) and an acid or diol. This reaction is carried out in the presence of a reaction catalyst. Suitable catalysts include trialkyl amines, monoalkyl diaryl amines, dialkylaryl amines, triaryl amines, trialkyl phosphines, monoalkyl diaryl phosphines, dialkyl aryl phosphines, trialkyl phosphines, quarternary ammonium compounds, quarternary phosphonium compounds, alkali metal halides, and the like. Quarternary ammonium or phosphonium compounds, and dialkyl aryl amines are preferred. In a preferred embodiment, the reaction catalyst is preferably present in an amount of at least 0.01 wt-%, and more preferably at least 0.1 wt-%, based on the weight of nonvolatile material in the coating composition. The reaction catalyst is preferably present in an amount of no greater than 3 wt-%, and more preferably no greater than 1 wt-%, based on the weight of nonvolatile material in the coating composition.
Coating compositions that include the urethane described herein are cured by crosslinking with one or more curing agents (i.e., crosslinking resins, sometimes referred to as “crosslinkers”). The choice of particular crosslinker typically depends on the particular product being formulated.
Suitable examples of such curing agents are hydroxyl-reactive curing resins such as phenoplasts, aminoplast, isocyanate-functional compounds, dianhydrides, or mixtures thereof.
Suitable phenoplast resins include the condensation products of aldehydes with phenols. Formaldehyde and acetaldehyde are preferred aldehydes. Various phenols can be employed such as phenol, cresol, p-phenylphenol, o-tert-butylphenol, p-tert-butylphenol, p-tert-amylphenol, cyclopentylphenol, and the like.
Suitable aminoplast resins are the condensation products of aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, furfural, benzaldehyde, and the like, with amino- or amido-group-containing substances such as urea, melamine, and benzoguanamine. Examples of suitable aminoplast crosslinking resins include, without limitation, benzoguanamine-formaldehyde resins, melamine-formaldehyde resins, etherified melamine-formaldehyde, and urea-formaldehyde resins.
Suitable isocyanate-functional compounds include, without limitation, blocked or unblocked aliphatic, cycloaliphatic or aromatic di-, tri-, or poly-valent isocyanates, such as hexamethylene diisocyanate, isophorone diisocyanate and the like. Further non-limiting examples of generally suitable unblocked or blocked isocyanates include isomers of isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, tetramethyl xylene diisocyanate, xylylene diisocyanate, and mixtures thereof. In some embodiments, unblocked or blocked isocyanates are used that have an Mn of at least about 300, more preferably at least about 650, and even more preferably at least about 1,000.
Polymeric unblocked or blocked isocyanates are useful in certain embodiments. Some examples of suitable polymeric blocked isocyanates include a biuret or isocyanurate of a diisocyanate, a trifunctional “trimer,” or a mixture thereof. Examples of suitable blocked polymeric isocyanates include TRIXENE BI 7951, TRIXENE BI 7984, TRIXENE BI 7963, TRIXENE BI 7981 (TRIXENE materials are available from Baxenden Chemicals, Ltd., Accrington, Lancashire, England), DESMODUR BL 3175A, DESMODUR BL3272, DESMODUR BL3370, DESMODUR BL 3475, DESMODUR BL 4265, DESMODUR PL 340, DESMODUR VP LS 2078, DESMODUR VP LS 2117, and DESMODUR VP LS 2352 (DESMODUR materials are available from Bayer Corp., Pittsburgh, Pa., USA), or combinations thereof.
Suitable dianhydrides include, without limitation, anhydrides of saturated and unsaturated carboxylic acids.
The level of curing agent (i.e., crosslinker) used will typically depend on the type of curing agent, the time and temperature of the bake, the molecular weight of the binder polymer, and the desired coating properties. If used, the crosslinker is typically present in an amount of up to 50 wt %, preferably up to 30 wt %, and more preferably up to 15 wt-%. If used, a crosslinker is preferably present in an amount of at least 0.1 wt %, more preferably at least 1 wt-%, and even more preferably at least 1.5 wt %. These weight percentages are based upon the total weight of the resin solids in the coating composition.
Accordingly, in a preferred embodiment, the present invention provides a urethane coating composition that includes a polyol derived from resins of formula (I) as described above, and a curing agent or crosslinker. In an embodiment, the crosslinker is preferably an isocyanate-functional compound as described above, such as, for example, polyisocyanates such as 2,4-toluenediisocyanate, hexamethylenediisocyanate, polymethylene-polyphenyl diisocyanate, methylenediphenyldiisocyanate, cyclic trimers, cocyclic trimers, or mixtures thereof. In a preferred embodiment, the isocyanate-functional crosslinker is a trimer. Examples of suitable trimers include, without limitation, trimerization products prepared from on average three diisocyanate molecules or a trimer prepared from on average three moles of diisocyanate (e.g., HMDI) reacted with one mole of another compound such as, for example, a triol (e.g., trimethylolpropane).
In an embodiment, a method of making a urethane coating composition is described herein. The method includes providing a resin of the general formula (I) and reacting it with an acid or a diol to provide a polyol. In an aspect, the acid or diol is present in an amount sufficient to react all epoxide groups present in the resin of formula (I). In another aspect, the reaction is carried out in the presence of a reaction catalyst.
In an embodiment, the polyol formed by reaction of the resin of formula (I) with an acid or diol has a theoretical hydroxyl equivalent weight of about 100 to 400, preferably 150 to 350. In an embodiment, the polyol has a hydroxyl (OH) number of about 100 to 400, preferably 150 to 350.
In a preferred embodiment, a polyol formed by the reaction of a resin of general formula (I) with an acid has a theoretical hydroxyl equivalent weight of about 300 to 350, preferably 300 to 320, and a hydroxyl (OH) number of about 150 to 250, preferably 175 to 200. In an alternative preferred embodiment, a polyol formed by the reaction of a resin of general formula (I) with a diol has a theoretical hydroxyl equivalent weight of about 150 to 250, preferably about 170 to 200, and a hydroxyl (OH) number of about 200 to 400, preferably 300 to 350.
In an embodiment, the reaction of a resin of general formula (I) with an acid or diol results in a reaction product (i.e. the polyol described herein) having a non-volatile solids concentration of about 70 to 80%, and a viscosity of about 1000 to 5000 centipoise (Gardner viscosity of approximately X to Z-3).
The reaction to produce the polyol is carried out a temperature of about 50° C. to 250° C., preferably from 100° C. to 200° C., for about 2 hours to 15 hours, preferably 4 hours to 12 hours. Reaction temperatures and time can vary substantially, but are selected to obtain a polyol where substantially all epoxide groups in the resin of general formula (I) have been reacted.
In the methods described herein, the formed polyol is cured by crosslinking with an isocyanate-functional compound to produce a urethane coating composition. In an embodiment, the isocyanate-functional compound is used in an amount sufficient to produce an OH:NCO ratio from 1:1 to 3:1. In an embodiment, where the polyol is formed by the reaction of a resin of formula (I) with an acid, the OH:NCO ratio is preferably 3:1, more preferably 2.82:1. In another embodiment, where the polyol is formed by the reaction of a resin of formula (I) with a diol, the OH:NCO ratio is preferably 2:1, more preferably 1.63:1.
The present description is directed to a urethane composition that can be used as a corrosion-resistant coating applied to a substrate, preferably a metal substrate such as, for example, cold-rolled steel (CRS), iron phosphate-treated steel, or aluminum. In an aspect, the urethane coating composition may be used as a corrosion-resistant primer, pretreatment or direct-to-metal coating. In a preferred aspect, the urethane composition can be used to form a corrosion-resistant coating when applied directly to a metal substrate without the use of a primer or pretreatment, i.e. as a direct-to-metal coating. Conventionally, direct-to-metal coatings show poor or inconsistent adhesion over various substrates. Therefore, for optimal corrosion resistance, high quality pretreatments are applied to the metal substrate before the application of the direct-to-metal coating. Without pretreatment, the metal substrate shows poor corrosion resistance and significant blistering in a humid environment. Surprisingly, and in contravention of expectations in the art, the urethane coating composition described herein demonstrates good corrosion resistance without any blistering over various metal substrates when used as a direct-to-metal coating.
Conventionally, polyols derived from epoxy resins are used to make urethane coating compositions that provide good adhesion. However, such coatings do not typically provide optimal corrosion resistance or good weathering, with significant yellowing of the coating observed on exposure to uv radiation. Surprisingly, and contrary to expectations in the art, the urethane coating composition described herein, which is made from an epoxy resin-derived polyol, demonstrates excellent corrosion resistance as well as good weathering. Moreover, the urethane coating described herein has high gloss and retains strong color and gloss even after significant or prolonged uv exposure.
As discussed above, in certain preferred embodiments, the coating composition of the present invention is suitable as a corrosion-resistant direct-to-metal coating. Without limiting to theory, it is believed that the corrosion resistance of the coating composition described herein may depend on the glass transition temperature (Tg) of the urethane polymer. In an embodiment, the urethane polymer of the present invention preferably has Tg of at least 25° C., more preferably at least 30° C., and even more preferably at least 40° C. In preferred embodiments, the Tg is less than 100° C., more preferably less than 80° C., and even more preferably less than 60° C. Varying the Tg, for example by varying the structure of the resins of general formula (I), or by varying the isocyanate-functional crosslinker, can provide coating compositions with different properties for use in different applications. A different range of Tg may be necessary if the urethane composition described herein is subject to an e-coat cure rather than a forced air dry, for example.
The polymers of the present invention can be applied to a substrate as part of a coating composition that includes a liquid carrier. The liquid carrier may be water, organic solvent, or mixtures of various such liquid carriers. Accordingly, liquid coating compositions of the present invention may be either water-based or solvent-based systems. Examples of suitable organic solvents include glycol ethers, alcohols, aromatic or aliphatic hydrocarbons, dibasic esters, ketones, esters, and the like, and combinations thereof. Preferably, such carriers are selected to provide a dispersion or solution of the polymer for further formulation. In an aspect, the properties of the urethane coating composition described herein may be altered if the coating is a high solids coating, i.e. the resin of general formula (I) is a solid resin rather than a liquid resin. In a preferred aspect, the coating composition described herein is dispersed in a liquid carrier and applied by standard commercial methods known in the art, such as for example, spraying, electrocoating, extrusion coating, laminating, powder coating, and the like.
The amount of the urethane polymer in the composition described herein may vary depending on a variety of considerations such as, for example, the method of application, the presence of other film-forming materials, whether the coating composition is water-based or solvent-based, etc. For liquid-based coating compositions, the urethane composition described herein will typically constitute at least 10 wt %, more typically at least 30 wt %, and even more typically at least 50 wt % of the coating composition, based on the total weight of resin solids in the coating composition.
In one embodiment, the coating composition is an organic solvent-based composition preferably having at least 50 wt % non-volatile components (i.e. solids), more preferably at least 60 wt % non-volatile components, and most preferably at least 70 wt % non-volatile components. In an embodiment, the non-volatile film-forming components preferably include at least 50 wt % of the urethane polymer described herein, more preferably at least 55 wt % of the polymer, and even more preferably at least 60 wt % of the polymer. For this embodiment, the non-volatile film-forming components preferably include no greater than 95 wt % of the polymer of the present invention, and more preferably no greater than 85 wt % of the polymer.
A coating composition of the present invention may also include other optional ingredients that do not adversely affect the coating composition or a cured coating composition resulting therefrom. Such optional ingredients are typically included in a coating composition to enhance coating aesthetics; to facilitate manufacturing, processing, handling, and application of the composition; and to further improve a particular functional property of a coating composition or a cured coating composition resulting therefrom. For example, the composition described herein invention may optionally include fillers, catalysts, lubricants, pigments, surfactants, dyes, colorants, toners, coalescents, extenders, anticorrosion agents, flow control agents, thixotropic agents, dispersing agents, antioxidants, adhesion promoters, light stabilizers, and mixtures thereof, as required to provide the desired film properties. Each optional ingredient is preferably included in a sufficient amount to serve its intended purpose, but not in such an amount to adversely affect a coating composition or a cured coating composition resulting therefrom.
Useful optional ingredients include pigments, such as, for example, titanium dioxide, iron oxide yellow, and the like. Suitable pigments for use with the composition described herein are known to those of skill in the art, and may be varied for a desired coating color or appearance. If used, a pigment is present in the coating composition in an amount of no greater than 70 wt %, more preferably no greater than 50 wt %, and even more preferably no greater than 40 wt %, based on the total weight of solids in the coating composition.
Wetting agents, dispersing agents and surfactants may be optionally added to the coating composition to aid in flow and wetting of the substrate. Examples of surfactants, include, but are not limited to, nonylphenol polyethers and salts and similar surfactants known to persons skilled in the art. If used, a surfactant is preferably present in an amount of at least 0.01 wt-%, and more preferably at least 0.1 wt-%, based on the weight of resin solids. If used, a surfactant is preferably present in an amount no greater than 10 wt-%, and more preferably no greater than 5 wt-%, based on the weight of resin solids.
The coating composition described herein may be used as a direct-to-metal coating, and the composition may be applied as a single layer, as two layers, or even multiple layers. Alternatively, the coating composition may also be used as a primer coating, a pretreatment coating, an intermediate coating, or a topcoat. The coating thickness of a particular layer and the overall coating system will vary depending upon the coating material used, the substrate, the coating application method, and the end use for the coated article. When used as a direct-to-metal coating, the thickness of the applied coating film is preferably about 0.5 to 3 mil, more preferably 1 to 2 mil, and even more preferably 1.2 to 1.8 mil.
The coating composition of the present invention may be applied to a substrate either prior to, or after, the substrate is formed into an article.
After applying the coating composition onto a substrate, the composition can be cured using a variety of processes, including, for example, oven baking by either conventional or convectional methods, or any other method that provides an elevated temperature suitable for curing the coating. The curing process may be performed in either discrete or combined steps.
The cure conditions will vary depending upon the method of application and the intended end use. The curing process may be performed at any suitable temperature, including, for example, oven temperatures in the range of from about 100° C. to about 300° C., and more typically from about 177° C. to about 250° C.
Unless indicated otherwise, the following test methods were utilized in the Examples that follow.
Adhesion testing is performed according to ASTM D 3359—Test Method B. Adhesion is generally rated on a scale of 0B to 5B where a rating of “5B” indicates no adhesion failure, i.e. no loss of paint from a crosshatch, a rating of “2B” indicates 15 to 35% paint loss from the crosshatch, and a rating of “0B” indicates greater than 65% paint loss from the crosshatch. Adhesion ratings of 5B and no less than 4B are typically desired for commercially viable coatings.
The direct and reverse impact resistance of cured coatings is tested using the methods described in ASTM D2794 (Standard Test Method for Resistance of Organic Coatings to the Effects of Rapid Deformation). Briefly, the coatings to be tested are applied to metal panels and cured. A standard weight is dropped a specific distance to strike an indenter that deforms the cured coating and the substrate to which it is applied. Results are expressed as the weight (in lb) dropped when the coating fails, typically by cracking.
The corrosion resistance of cured coatings prepared from the composition described herein is tested using the salt fog method, as described in ASTM B117 (Standard Practice for Operating Salt Fog Apparatus). Results are expressed on a scale of 0-10, where “0” indicates the coating is completely corroded, observed by bubbling or blistering of the film in all areas, and “10” indicates the coating is unchanged from before it was subjected to the corrosive environment. Rust ratings for coatings subjected to salt fog exposure in a humid environment are also expressed on a scale of 0-10 where “0” indicates complete surface rust, and “10” indicates no surface rust.
The corrosion resistance of cured coatings prepared from the composition described herein is also tested by measuring creep after exposure to a corrosive environment, as described in ASTM D1654-08 (Standard Test Method for Evaluation of Painted or Coated Specimens Subjected to Corrosive Environments). A coating is applied to a panel and cured. The panel is then scribed to metal and exposed to salt fog for a given period of time. Paint loss from the scribe is measured, and results are expressed as the amount of creep (in mm) from the scribe. For commercially viable coatings, creep from scribe of 3 mm or less is desired.
The flexibility of cured coatings prepared from the composition described herein is tested using the mandrel bend test, as described in ASTM D522 (Standard Test Methods for Mandrel Bend test for Attached Organic Coatings). Results are expressed as the length (in mm) to which a coating film can be elongated (or bent) before the film cracks.
The hardness of cured coatings prepared from the powder compositions is tested using by the pencil method, as described in ASTM D3363 (Standard Test Method for Film Hardness by Pencil Test). Results are reported in terms of the last successful pencil prior to film rupture. Thus, for example, if a coating does not rupture when tested with a 2H pencil, but ruptures when tested with a 3H pencil, the coating is reported to have a pencil hardness of 2H.
For the present evaluation, coatings were applied to panels of various substrates at a film thickness of about 1.4 mil and subjected to the tests described above.
The following examples are offered to aid in understanding of the present invention and are not to be construed as limiting the scope thereof. Unless otherwise indicated, all parts and percentages are by weight. The constructions cited were evaluated by tests as follows:
A solution of 1059 g of a novolac epoxy resin (obtained from Dow) in methylethyl ketone or MEK was charged into a 4-neck, 3-liter round bottom flask, along with 610 g (approximately 5 moles) of benzoic acid in the presence of 1.5 g of tetramethyl ammonium chloride as a catalyst. The mixture was heated under a nitrogen blanket to a temperature of 130° C. and the MEK was allowed to boil off during the course of the reaction and was collected through a condenser. The reaction was sampled after four hours and the epoxy value was measured to be 10. The residual MEK was stripped off and 647 g of butyl acetate were added slowly through an additional funnel while the reactants were cooled to room temperature. The resulting reaction product was a polyol resin with 71.5% non-volatile content and a Gardner viscosity of X. The theoretical hydroxy equivalent (on a 100% solids basis) was 302, corresponding to OH number of 187.
To prepare a urethane composition or paint with the polyol #1 (prepared as described in Example 1), 10.07 g of butyl acetate was added to a metal container, followed by 144.07 g of polyol #1. An additional quantity of butyl acetate was then added with agitation, along with the pigments, dispersing agents, flocculating agents and the like, required to formulate a paint of a specific volume. The mixture was ground in a horizontal media mill to a Hegman grind of 7. The mixture was let down into 17.09 g butyl acetate with slow agitation, and 346.20 g of polyol #1 was added, along with 94.82 g of butyl acetate, an acrylic-based tint paste, dibutyltindilaurate as a stabilizer, flow agents, pigments, and an adhesion promoter. The paint formulation was then mixed with a commercially available standard HDI trimer at a paint:isocyanate ratio of 2.82:1.
A solution of 752 g of a conventional epoxy resin derived from BPA (EPON 828, obtained from Momentive) was charged into a 4-neck, 3-liter round bottom flask, along with 540 g of 1,4-butanediol in the presence of 1.5 g of dimethylbenzyl amine as a catalyst. The mixture was heated under a nitrogen blanket to a temperature of 190° C. and reacted for 12 hours. The reaction was sampled and the epoxy value was measured to be 11.5. The reactor contents were cooled to 120° C. and 681 g of butyl acetate were added slowly through an addition funnel while the reactants were cooled to room temperature. The resulting reaction product was a polyol resin with 72.9% non-volatile content and a Gardner viscosity of Z3. The theoretical hydroxy equivalent (on a 100% solids basis) was 170, corresponding to OH number of 330.
To prepare a urethane composition or paint with the polyol #2 (prepared as described in Example 3), 10.00 g of butyl acetate were added to a metal container, followed by 144.07 g of polyol #2. An additional quantity of butyl acetate was then added with agitation, along with the pigments, dispersing agents, flocculating agents, catalysts and the like, required to formulate a paint of a specific volume. The ingredients were thoroughly mixed and the mixture was ground in a horizontal media mill to a Hegman grind of 7. The ground mixture was let down into 17.09 g butyl acetate with slow agitation, and 154.7 g of polyol #2 were added, along with 67.06 g of butyl acetate, an acrylic-based tint paste, dibutyltindilaurate as a stabilizer, flow agents, pigments, and an adhesion promoter. The paint formulation was then mixed with a commercially available standard HDI trimer at a paint:isocyanate ratio of 1.63:1.
The paints from Examples 2 and 4 were sprayed onto unprimed or un-pretreated panels of cold rolled steel (CRS), aluminum or phosphate-treated steel, at an applied film build of about 1.4 mil. The sprayed panels were then flashed for 10 minutes and baked for 30 minutes at 180° F. The panels were scribed to metal and exposed to salt for 240 hours, followed by evaluation of various mechanical and physical properties. Results are shown in Table 1.
The complete disclosure of all patents, patent applications, and publications, and electronically available material cited herein are incorporated by reference. The foregoing detailed description and examples have been given for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described, for variations obvious to one skilled in the art will be included within the invention defined by the claims. The invention illustratively disclosed herein suitably may be practiced, in some embodiments, in the absence of any element which is not specifically disclosed herein.
The present application is a continuation of International Application No. PCT/US2014/039196, filed on May 22, 2014, which claims priority from U.S. Provisional Application Ser. No. 61/832,254, filed 7 Jun. 2013, each of which is incorporated by reference herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61832254 | Jun 2013 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14953972 | Nov 2015 | US |
| Child | 16551189 | US | |
| Parent | PCT/US2014/039196 | May 2014 | US |
| Child | 14953972 | US |
