Source: http://www.google.com/patents/US6160058?dq=5,241,671
Timestamp: 2015-04-22 00:19:48
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Matched Legal Cases: ['application No. 08', 'application No. 08', 'application No. 60', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08']

Patent US6160058 - Composition including component having at least one carbamate group or urea ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsThe present invention provides a curable coating composition that includes at least three components. The coating composition includes a component (a) that includes one or both of a compound (a)(1) having at least one carbamate group or terminal urea group according to the invention and having at least...http://www.google.com/patents/US6160058?utm_source=gb-gplus-sharePatent US6160058 - Composition including component having at least one carbamate group or urea group, acrylic polymer comprising active hydrogen-containing functional groups reactive with third component, curing agent reactive with both componentsAdvanced Patent SearchPublication numberUS6160058 APublication typeGrantApplication numberUS 09/184,196Publication dateDec 12, 2000Filing dateNov 2, 1998Priority dateJul 28, 1993Fee statusPaidAlso published asCA2346101A1, CA2346101C, DE69904638D1, DE69904638T2, EP1124909A1, EP1124909B1, WO2000026315A1Publication number09184196, 184196, US 6160058 A, US 6160058A, US-A-6160058, US6160058 A, US6160058AInventorsWalter H. Ohrbom, Gregory G. Menovcik, Donald L. St. Aubin, John E. Boisseau, John W. RehfussOriginal AssigneeBasf CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (1), Referenced by (13), Classifications (99), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetComposition including component having at least one carbamate group or urea group, acrylic polymer comprising active hydrogen-containing functional groups reactive with third component, curing agent reactive with both components
US 6160058 AAbstract
The present invention provides a curable coating composition that includes at least three components. The coating composition includes a component (a) that includes one or both of a compound (a)(1) having at least one carbamate group or terminal urea group according to the invention and having at least two linking groups that are urethane or urea or a compound (a)(2) having at least two groups selected from carbamate groups, terminal urea groups, or combinations of the two and at least four urethane or urea linking groups. The second component (b) of the coating composition includes an acrylic polymer comprising active hydrogen-containing functional groups reactive with the third component(c). Component (c) of the coating composition is a curing agent that is reactive with the first two components. Preparation of coated articles using the compositions of the invention is also disclosed.
1. A curable coating composition, comprising(a) a component selected from the group consisting of:(1) a compound having at least one carbamate group or urea group that is prepared by a step of reacting a mixture comprising:(A) a compound comprising a carbamate or urea group or a group that can be converted to a carbamate or urea group and a group that is reactive with (a)(1)(B) and (B) a polyisocyanate, (2) a compound having at least one carbamate group or urea group that is prepared by a step of reacting a mixture comprising:(A) a compound comprising a carbamate or urea group or a group that can be converted to a carbamate or urea group and an isocyanate group and (B) a compound having at least two groups reactive with isocyanate functionality,and mixtures thereof; (b) an acrylic polymer comprising active hydrogen-containing functional groups that are reactive with component (c), and (c) a curing agent that is reactive with compound (a) and compound (b),wherein said carbamate group has a structure ##STR13## in which R is H or alkyl, and further wherein said urea group has a structure ##STR14## in which R' and R" are each independently H or alkyl, or R' and R" together form a heterocyclic ring structure. 2. A composition according to claim 1, wherein component (a) has at least one carbamate group.
7. A composition according to claim 3, wherein compound (a) (1) (A) has a carbamate group.
9. A composition according to claim 3, wherein compound (a)(1) (A) is a hydroxyalkyl cyclic carbonate.
24. A composition according to claim 1, wherein component (b) has functionality selected from the group consisting of carbamate functionality, urea functionality, hydroxyl functionality, and combinations thereof.
25. A composition according to claim 1, wherein component (b) has functionality selected from the group consisting of carbamate functionality, hydroxyl functionality, and combinations thereof.
26. A composition according to claim 1, wherein component (b) has carbamate functionality.
27. A composition according to claim 1, wherein component (b) has hydroxyl functionality.
36. An article according to claim 15, wherein said substrate is a flexible substrate.
37. A curable coating composition, comprising(a) a compound selected from the group consisting of compounds having structures ##STR15## and mixtures thereof; and (b) an acrylic polymer comprising active hydrogen-containing functional groups that are reactive with component (c), and (c) a curing agent that is reactive with compound (a) and component (b),wherein R is H or alkyl; R' and R" are each independently H or alkyl, or R' and R" together form a heterocyclic ring structure; R2 is alkylene or substituted alkylene; R1, R3, R5, and R6 are independently alkylene, cycloalkylene, or arylalkylene, or R3, R5, and R5 are independently arylene, or a structure that includes a cyanuric ring, a urethane group, a urea group, a carboduimide group, a biuret structure, or an allophonate group; n is from 0 to about 10; m is from 2 to about 6; and L is O, NH, or NR4, where R4 is an alkyl; in which p is from 1 to 5, and m+p is 2 to 6; in which R5 and R6 are each independently alkylene, cycloalkylene, alkylarylene, or arylene, or R6 is a structure that includes a cyanuric ring, a biuret structure, or an allophonate group. Description
The present application is a continuation-in-part of Green et al, U.S. application No. 08/997,317, filed Dec. 23, 1997, now U.S. Pat. No. 5,994,479, which is continuation-in-part of each of the following: Green et al., U.S. application No. 08/886,321, filed Jul. 1, 1997, now U.S. Pat. No. 5,872,195, which is a continuation of provisional application No. 60/021,068, filed Jul. 1, 1996; McGee et al., U.S. application No. 08/698,529, filed Aug. 15, 1996, now U.S. Pat. No. 5,854,385, which is a continuation of Ser. No. 08/540,274, filed Oct. 6, 1995, now abandoned; Menovcik et al., U.S. application No. 08/333,917, filed Nov. 3, 1994, now U.S. Pat. No. 5,744,550, issued Apr. 28, 1998; U.S. application No. 08/176,608, filed Jan. 3, 1994, now abandoned; Rehfuss et al., U.S. application No. 08/287,351, filed Aug. 8, 1994, now abandoned which is a continuation-in-part of Ser. No. 08/098,177, filed Jul. 28, 1993, now abandoned; McGee et al., U.S. application No. 08/867,547, filed Jun. 2, 1997, now abandoned which is a continuation of U.S. application No. 08/513,587, filed Aug. 10, 1995, now U.S. Pat. No. 5,726,244, issued Mar. 10, 1998; Menovcik et al., U.S. application No. 08/547,513, filed Oct. 24, 1995, now U.S. Pat. No. 5,726,274, issued Mar. 10, 1998, which is a division of U.S. application No. 08/361,344, filed Dec. 21, 1994, now abandoned; Menovcik et al., U.S. application No. 08/547,174, filed Oct. 24, 1995, now U.S. Pat. No. 5,723,552, issued Mar. 3, 1998, which is a divisional of U.S. application No. 08/361,344, filed Dec. 21, 1994, now abandoned; Menovcik et al., U.S. application No. 08/698,524, filed Aug. 15, 1996, now U.S. Pat. No. 5,792,810, issued Aug. 11, 1998, which is a continuation of Ser. No. 08/550,880, filed Oct. 6, 1995; Bammel et al., U.S. application No. 08/698,526, filed Aug. 15, 1996, now U.S. Pat. No. 5,760,127, issued Jun. 2, 1998, which is a continuation of U.S. application No. 08/686,929, filed Oct. 6, 1995 now pending; Ohrbom et al., U.S. application No. 08/667,261, filed Jun. 20, 1996, now U.S. Pat. No. 5,777,048, issued Jul. 7, 1998; Ohrbom et al., U.S. application No. 08/698,528, filed Aug. 15, 1996, now U.S. Pat. No. 5,756,213, issued May 26, 1998, which is a continuation of U.S. application No. 08/540,275, filed Oct. 6, 1995, now abandoned; Ohrbom et., al., U.S. application No. 08/698,522, filed Aug. 15, 1996, now U.S. Pat. No. 5,827,930, which is a continuation of U.S. application No. 08/540,277, filed Oct. 6, 1995, now abandoned; McGee et al., U.S. application No. 08/698,523, filed Aug. 15, 1996, now U.S. Pat. No. 5,770,650, issued Jun. 23, 1998, which is a continuation of U.S. application No. 08/540,279, filed Oct. 6, 1995, now abandoned; Green et al., U.S. application No. 08/886,321, filed Jul. 1, 1997, now U.S. Pat. No. 5,872,195, which is a continuation of provisional application 60/021,068, filed Jul. 1, 1996; Bammel et al., U.S. application No. 08/831,810, filed Apr. 2, 1997 now pending; Ohrbom et al, U.S. application No. 08/333,804, filed Nov. 3, 1994 now pending.
Curable coating compositions utilizing carbamate-functional resins are described, for example, in U.S. Pat. Nos. 5,693,724, 5,693,723, 5,639,828, 5,512,639, 5,508,379, 5,451,656, 5,356,669, 5,336,566, and 5,532,061, and U.S. application Nos. 08/886,321, filed Jul. 1, 1997, 08/698,529, filed Aug. 15, 1996, 08/719,670, filed Sep. 25, 1996, 08/166,277, filed Dec. 13, 1993, 08/339,999, filed Nov. 15, 1994, 08/333,917, filed Nov. 3, 1994, 08/176,608, filed Jan. 3, 1994, 08/287,351, filed Aug. 8, 1994, 08/804,239, filed Feb. 20, 1997, 08/333,804, filed Nov. 3, 1994, 08/884,613, filed Jun. 30, 1997, 08/885,638, filed Jun. 30, 1997, 08/513,587, filed Aug. 10, 1995, 08/867,547, filed Jun. 2, 1997, 08/547,514, filed Oct. 24, 1994, 08/547,513, filed Oct. 24, 1994, 08/547,174, filed Oct. 24, 1994, 08/698,524, filed Aug. 15, 1996, 08/698,526, filed Aug. 15, 1996, 08/667,261, filed Jun. 20, 1996, 08/698,528, filed Aug. 15, 1996, 08/698,522, filed Aug. 15, 1996, 08/698,572, filed Aug. 15, 1996, 08/698,523, filed Aug. 15, 1996, 08/673,935, filed Jul. 1, 1996, 08/886,321, filed Jul. 1, 1997, and 08/831,810, filed Apr. 2, 1997, each of which is incorporated herein by reference. These coating compositions can provide significant etch advantages over other coating compositions, such as hydroxy-functional acrylic/melamine coating compositions. It may often be desirable, however, to provide still further improvements in the above-described coating properties.
Component (a) includes one or both of two compounds, compounds (a)(1) and (a)(2) having at least one carbamate group or terminal urea group. When used in connection with the invention, the term "carbamate group" refers to a group having a structure ##STR1## in which R is H or alkyl. Preferably, R is H or alkyl of from 1 to about 4 carbon atoms, and more preferably R is H. When used in connection with the invention, "terminal urea group" refers to a group having a structure ##STR2## in which R' and R" are each independently H or alkyl, or R' and R" together form a heterocyclic ring structure. Preferably, R' and R" are each independently H or alkyl of from 1 to about 4 carbon atoms or together form an ethylene bridge, and more preferably R' and R" are each independently H. The terminal urea group of the invention is distinguished from urea linking groups for which R" would be other than alkyl.
Compound (a)(1) has at least one carbamate group or terminal urea group and at least two linking groups that are urethane or urea. Preferred compounds (a)(1) may be represented by any of the structures ##STR3## in which R, R', and R" are as previously defined; R1 is alkylene or arylalkylene, preferably alkylene, and particularly alkylene of 5 to 10 carbon atoms; R2 is alkylene or substituted alkylene, preferably having from about 2 to about 4 carbon atoms; R3 is alkylene (including cycloalkylene), alkylarylene, arylene, or a structure that includes a cyanuric ring, a urethane group, a urea group, a carbodiimide group, a biuret structure, or an allophonate group, preferably alkylene (including cycloalkylene) or a structure that includes a cyanuric ring; n is from 0 to about 10, preferably from 0 to about 5; m is from 2 to about 6, preferably 2 or 3; and L is O, NH, or NR4, where R4 is an alkyl, preferably an alkyl of 1 to about 6 carbon atoms; p is from 1 to 5, preferably 1 or 2, and m+p is 2 to 6, preferably about 3. Preferably, R3 is alkylene (including cycloalkylene), alkylarylene, arylene, or a structure that includes a cyanuric ring.
Alternatively or in addition to this compound (a)(1), the component (a) may include a compound (a)(2) having at least two groups selected from carbamate groups, terminal urea groups, or combinations of the two and at least four urethane or urea linking groups. Preferred compounds (a)(2) may be represented by any of the structures ##STR4## in which R, R', and R" are as previously defined; R1 is alkylene or arylalkylene, preferably alkylene, and particularly alkylene of 5 to 10 carbon atoms; R2 is alkylene or substituted alkylene, preferably having from about 2 to about 4 carbon atoms; R3 is alkylene (including cycloalkylene), alkylarylene, arylene, or a structure that includes a cyanuric ring, a urethane group, a urea group, a carbodiimide group, a biuret structure, or an allophonate group, preferably alkylene (including cycloalkylene) or a structure that includes a cyanuric ring; n is from 0 to about 10, preferably from 0 to about 5; m is from 2 to about 6, preferably 2 or 3; and L is O, NH, or NR4, where R4 is an alkyl, preferably an alkyl of 1 to about 6 carbon atoms; p is from 1 to 5, preferably 1 or 2, and m+p is 2 to 6, preferably about 3. Preferably, R3 is alkylene (including cycloalkylene), alkylarylene, arylene, or a structure that includes a cyanuric ring.
The second component (b) of the coating composition is a polymer resin that includes a polyester, a polyurethane, and/or a polyester-polyurethane resin, with the resin or resins used for component (b) comprising active hydrogen-containing functional groups reactive with the third component(c).
The composition according to the present invention includes as a first component (a) a compound having at least one carbamate group or terminal urea group. First, the component (a) may include a compound (a)(1) having at least one carbamate group or terminal urea group and having at least two linking groups that are urethane or urea. Preferred compounds (a)(1) may be represented by any of the structures ##STR5## in which R, R', R", R2, R3, L, and m are as previously defined; p is from 1 to 5, preferably 1 or 2, and m+p is 2 to 6, preferably about 3. Preferably, R3 is alkylene (including cycloalkylene), alkylarylene, arylene, or a structure that includes a cyanuric ring. In one preferred embodiment R3 includes a member selected from the group of ##STR6## and mixtures thereof. L is particularly preferably an oxygen atom.
Other groups, such as hydroxyl groups or isocyanate groups can also be converted to carbamate groups. However, if hydroxyl groups were to be present on the compound and it is desired to convert those groups to carbamate after the reaction with the polyisocyanate (a)(1)(B), they would have to be blocked or protected so that they would not react during the reaction with compound (a)(1)(B) or else in stoichiometric excess so that some would be expected to remain unreacted for later conversion to the carbamate or terminal urea group(s). Conversion to carbamate or urea could also be carried out prior to the reaction with compound (a)(1)(A). Hydroxyl groups can be converted to carbamate groups by reaction with a monoisocyanate (e.g., methyl isocyanate) to form a secondary carbamate group (that is, a carbamate of the structure above in which R is alkyl) or with cyanic acid (which may be formed in situ by thermal decomposition of urea) to form a primary carbamate group (i.e., R in the above formula is H). This reaction preferably occurs in the presence of a catalyst as is known in the art. A hydroxyl group can also be reacted with phosgene and then ammonia to form a primary carbamate group, or by reaction of the hydroxyl with phosgene and then a primary amine to form a compound having secondary carbamate groups. Another approach is to react an isocyanate with a compound such as hydroxyalkyl carbamate to form a carbamate-capped isocyanate derivative. For example, one isocyanate group on toluene diisocyanate can be reacted with hydroxypropyl carbamate, followed by reaction of the other isocyanate group with an excess of polyol to form a hydroxy carbamate. Finally, carbamates can be prepared by a transesterification approach where hydroxyl group is reacted with an alkyl carbamate (e.g., methyl carbamate, ethyl carbamate, butyl carbamate) to form a primary carbamate group-containing compound. This reaction is performed at elevated temperatures, preferably in the presence of a catalyst such as an organometallic catalyst (e.g., dibutyltin dilaurate). Other techniques for preparing carbamates are also known in the art and are described, for example, in P. Adams & F. Baron, "Esters of Carbamic Acid", Chemical Review, v. 65, 1965.
Suitable compounds (a)(1)(A) include, without limitation, any of those compounds having a carbamate or terminal urea group and a hydroxyl or primary or secondary amine group. Illustrative examples of suitable compounds of this type include, without limitation, hydroxy alkyl carbamates and hydroxyalkylene alkyl ureas, such as hydroxyethyl carbamate, hydroxypropyl carbamate, and hydroxyethylene ethyl urea. Hydroxypropyl carbamate and hydroxyethyl ethylene urea, for example, are well known and commercially available. Amino carbamates are described in U.S. Pat. 2,842,523. Compounds with hydroxyl and terminal urea groups may also be prepared by reacting the amine group of an amino alcohol with hydrochloric acid and then urea to form a hydroxy terminal urea compound. An amino alcohol can be prepared, for example, by reacting an oxazolidone with ammonia. Amino terminal urea compounds can be prepared, for example, by reacting a ketone with a diamine having one amine group protected from reaction (e.g., by steric hindrance), followed by reaction with HNCO (e.g., as generated by thermal decomposition of urea), and finally reaction with water. Alternatively, these compounds can be prepared by starting with a compound having the group that can be converted to carbamate or terminal urea, which groups are described below, and converting that group to the carbamate or urea prior to beginning the reaction with the polyisocyanate (a)(1)(B).
Cyclic carbonates typically have 5- or 6-membered rings, as is known in the art. Five-membered rings are preferred, due to their ease of synthesis and greater degree of commercial availability. Six-membered rings can be synthesized by reacting phosgene with 1,3-propanediol under conditions known in the art for the formation of cyclic carbonates. Preferred hydroxyalkyl cyclic carbonates used in the practice of the invention can be represented by the formula: ##STR8## in which R (or each instance of R if n is more than 1) is a hydroxyalkyl group of 1-18 carbon atoms, preferably 1-6 carbon atoms, and more preferably 1-3 carbon atoms, which may be linear or branched and may have substituents in addition to the hydroxyl group, and n is 1 or 2, which may be substituted by one or more other substituents such as blocked amines or unsaturated groups. The hydroxyl group may be on a primary, secondary, or tertiary carbon. More preferably, R is --(CH2)p -- OH, where the hydroxyl may be on a primary or secondary carbon and p is 1 to 8, and even more preferably in which the hydroxyl is on a primary carbon and p is 1 or 2.
Compound (a)(1) may also be formed by a reaction mixture includes, in addition to compounds (a)(1)(A) and (a)(1)(B), a compound (a)(1)(C) that is an active-hydrogen chain extension agent. Chain extension agents may be used to increase the length of compound (a)(1) or to bridge together two or more products of the reaction of compounds (a)(1)(A) and (a)(1)(B). Useful active hydrogen-containing chain extension agents generally contain at least two, preferably about two, active hydrogen groups, for example, diols, dithiols, diamines, or compounds having a mixture of hydroxyl, thiol, and amine groups, such as alkanolamines, aminoalkyl mercaptans, and hydroxyalkyl mercaptans, among others. For purposes of this aspect of the invention, both primary and secondary amine groups are considered as having one active hydrogen. Active hydrogen-containing chain extension agents also include water. In a preferred embodiment of the invention, a polyol is used as the chain extension agent. In an especially preferred embodiment, a diol is used as the chain extension agent with little or no higher polyols, so as to minimize branching. Examples of preferred compounds (a)(1)(C) include, without limitation, 1,6-hexanediol, 1,2-hexanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 3-hydroxy-2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropionate (sold by Eastman Chemical Co. as Esterdiol 204), 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, cyclohexanedimethanol (sold as CHDM by Eastman Chemical Co.), ethyl-propyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 1,3-dihydroxyacetone dimer, 2-butene-1,4-diol, pantothenol, dimethyltartrate, pentaethylene glycol, dimethyl silyl dipropanol, and 2,2'-thiodiethanol. While polyhydroxy compounds containing at least three hydroxyl groups may be used as chain extenders, the use of these compounds may produce higher molecular weight, more branched compounds. Higher-functional polyhydroxy compounds include, for example, trimethylolpropane, trimethylolethane, pentaerythritol, among other compounds. In a particularly preferred embodiment, the monomeric isocyanate is a diisocyanate, especially isophorone or hexamethylene diisocyanate and an average of one of the isocyanate groups per molecule is reacted with the compound (a)(1)(A) comprising a group that is reactive with isocyanate and a carbamate group or group that can be converted into a carbamate group, preferably with hydroxypropyl carbamate, and the remaining isocyanate groups are reacted with a polyol, particularly with 2-ethyl-1,6-hexanediol. The reactions of the polyisocyanate with compounds (a)(1)(A) and (a)(1)(C) can be carried out in any order, including concurrently. While a mixture of reaction products may be expected each of the isocyanate groups has about the same reactivity, at least a part should be the idealized product in which a molecule of the polyisocyanate has reacted with both a compound (a)(1)(A) and a compound (a)(1)(C).
Instead of or in addition to the compound (a)(1), component (a) may include a compound (a)(2) having at least two carbamate and/or terminal urea groups and at least four urethane or urea linking groups. Preferred compounds (a)(2) may be represented by any of the structures ##STR9## in which R, R', R", R2, L, and m are as previously defined; R5 and R6 are each independently alkylene (including cycloalkylene), preferably having from 1 to about 18 carbon atoms, particularly preferably from about 5 to about 12 carbon atoms, alkylarylene, or arylene, or R6 is a structure that includes a cyanuric ring, a biuret structure, or an allophonate group.
The compound (a)(2)(A) preferably has, on average, one isocyanate group per molecule. The compound (a)(2)(A) also preferably has a carbamate or terminal urea group, and particularly preferably has a carbamate group. In one embodiment, compound (a)(2)(A) is a reaction product of an hydroxyalkyl carbamate and a polyisocyanate compound. In another embodiments, compound (a)(2)(A) is a reaction product of an hydroxyalkyl cyclic carbonate and a polyisocyanate compound. Preferably, a hydroxyalkyl carbamate and a polyisocyanate are reacted to produce an isocyanate-functional compound with carbamate functionality. In a particularly preferred embodiment, a β-hydroxyalkyl carbamate is reacted with one of the isocyanate groups of a diisocyanate, such as IPDI or HMDI, or with one or two of the isocyanate groups of an isocyanurate, such as the isocyanurate of HMDI or IPDI, to produce a compound (a)(2)(A) having both isocyanate and carbamate functionality.
Component (b) of the coating compositions of the invention includes an acrylic polymer. The acrylic polymer comprises active hydrogen-containing functional groups that are reactive with the third component (c) curing agent. Suitable active hydrogen-containing functional groups include, without limitation, hydroxyl functionality, acid functionality, carbamate functionality, terminal urea functionality, and combinations of these. In a preferred embodiment, the acrylic polymer (b) has carbamate or terminal urea functionality. The carbamate or terminal urea functionality may be introduced to the polymer by either polymerizing using a carbamate- or terminal urea-functional monomer or by reacting a functional group on the formed polymer in a further reaction to produce a carbamate or terminal urea functionality at that position. If the functional group on the acrylic polymer (b) is an isocyanate group, the group can be reacted with a hydroxyalkyl carbamate, or with a hydroxy-containing epoxide with the epoxy group subsequently converted to carbamate by reaction with CO2 and then ammonia. Preferably, an isocyanate-functional acrylic polymer is reacted with hydroxyethyl carbamate, hydroxypropyl carbamate, hydroxybutyl carbamate, or mixtures thereof. If the functional group is hydroxyl, the reactive group on the carbamate-containing compound may be oxygen of the C(═O) O portion of the carbamate group on an alkyl carbamate or methylol, such as with methylol acrylamide (HO--CH2 --NH--C(═O)--CH═CH2). In the case of the C(═O)O group on an alkyl carbamate, the hydroxyl group on the polymer undergoes a transesterification with the C(═O)O group, resulting in the carbamate group being appended to the polymer. In the case of methylol acrylamide, the unsaturated double bond is then reacted with peroxide, CO2, and ammonia as described above. If the functional group on the polymer is a carboxyl group, the acid group can be reacted with epichlorohydrin to form a monoglycidyl ester, which can be converted to carbamate by reaction with CO2, and then ammonia.
Carbamate functionality can also be introduced to the acrylic polymer of component (b) by reacting the polymer with a compound that has a group that can be converted to a carbamate, and then converting that group to the carbamate. Examples of suitable compounds with groups that can be converted to a carbamate include, without limitation, active hydrogen-containing cyclic carbonate compounds (e.g., the reaction product of glycidol and CO2) that are convertible to carbamate by reaction with ammonia, monoglycidyl ethers and esters convertible to carbamate by reaction with CO2 and then ammonia, allyl alcohols where the alcohol group is reactive with isocyanate functionality and the double bond can be converted to carbamate by reaction with peroxide, and vinyl esters where the ester group is reactive with isocyanate functionality and the vinyl group can be converted to carbamate by reaction with peroxide, then CO2, and then ammonia. Any of the above compounds can be utilized as compounds containing carbamate groups rather than groups convertible to carbamate by converting the group to carbamate prior to reaction with the polymer.
One way to prepare such polymers is to prepare an acrylic monomer having a carbamate functionality in the ester portion of the monomer. Such monomers are well-known in the art and are described, for example in U.S. Pat. Nos. 3,479,328, 3,674,838, 4,126,747, 4,279,833, and 4,340,497, 5,356,669, and WO 94/10211, the disclosures of which are incorporated herein by reference. One method of synthesis involves reaction of a hydroxy-functional monomer with cyanic acid (which may be formed by the thermal decomposition of urea) to form the carbamyloxy carboxylate (i.e., carbamate-modified (meth)acrylate). Another method of synthesis reacts an α, β-unsaturated acid ester with a hydroxy carbamate ester to form the carbamyloxy carboxylate. Yet another technique involves formation of a hydroxyalkyl carbamate by reacting a primary or secondary amine or diamine with a cyclic carbonate such as ethylene carbonate. The hydroxyl group on the hydroxyalkyl carbamate is then esterified by reaction with acrylic or methacrylic acid to form the monomer. Other methods of preparing carbamate-modified acrylic monomers are described in the art, and can be utilized as well. The acrylic monomer can then be polymerized along with other ethylenically-unsaturated monomers, if desired, by techniques well-known in the art.
An alternative route for preparing a carbamate-functional polymer is to react an already-formed polymer such as an acrylic polymer with another component to form a carbamate-functional group appended to the polymer backbone, as described in U.S. Pat. No. 4,758,632, the disclosure of which is incorporated herein by reference. One technique for preparing acrylic polymers useful as the second component involves thermally decomposing urea (to give off ammonia and HNCO) in the presence of a hydroxy-functional acrylic polymer to form a carbamate-functional acrylic polymer. Another technique involves reacting the hydroxyl group of a hydroxyalkyl carbamate with the isocyanate group of an isocyanate-functional acrylic or vinyl monomer to form the carbamate-functional acrylic. Isocyanate-functional acrylics are known in the art and are described, for example in U.S. Pat. No. 4,301,257, the disclosure of which is incorporated herein by reference. Isocyanate vinyl monomers are well-known in the art and include unsaturated m-tetramethyl xylene isocyanate and isocyanatoethyl methacrylate. Yet another technique is to react the cyclic carbonate group on a cyclic carbonate-functional acrylic with ammonia in order to form the carbamate-functional acrylic. Cyclic carbonate-functional acrylic polymers are known in the art and are described, for example, in U.S. Pat. No. 2,979,514, the disclosure of which is incorporated herein by reference. Another technique is to transcarbamylate a hydroxy-functional acrylic polymer with an alkyl carbamate. A more difficult, but feasible way of preparing the polymer would be to trans-esterify an acrylate polymer with a hydroxyalkyl carbamate.
Modified acrylics can also be used as the polymer (b) according to the invention. Such acrylics may be polyester-modified acrylics or polyurethane-modified acrylics, as is well-known in the art. Polyester-modified acrylics modified with ε-caprolactone are described in U.S. Pat. No. 4,546,046 of Etzell et al., the disclosure of which is incorporated herein by reference. Polyurethane-modified acrylics are also well-known in the art. They are described, for example, in U.S. Pat. No. 4,584,354, the disclosure of which is incorporated herein by reference.
The coating compositions described herein are preferably subjected to conditions so as to cure the coating layers. Although various methods of curing may be used, heat-curing is preferred. Generally, heat curing is effected by exposing the coated article to elevated temperatures provided primarily by radiative heat sources. Curing temperatures will vary depending on the particular blocking groups used in the cross-linking agents, however they generally range between 90� C. and 180� C.. The first compounds according to the present invention are preferably reactive even at relatively low cure temperatures. Thus, in a preferred embodiment, the cure temperature is preferably between 115� C and 150� C., and more preferably at temperatures between 115� C. and 140� C. for a blocked acid catalyzed system. For an unblocked acid catalyzed system, the cure temperature is preferably between 80� C. and 100� C.. The curing time will vary depending on the particular components used, and physical parameters such as the thickness of the layers, however, typical curing times range from 15 to 60 minutes, and preferably 15-25 minutes for blocked acid catalyzed systems and 10-20 minutes for unblocked acid catalyzed systems.
A mixture of 278.1 parts by weight of methyl isoamyl ketone, 1272.8 parts by weight of T1890-A (isocyanurate of isophorone diisocyanate, available from CreaNova), and 0.7 parts by weight of dibutyl tin dilaurate was heated in a suitable reaction vessel to 40� C. under an inert atmosphere. Next, 463.5 parts by weight of beta-hydroxy butyl carbamate was added, followed by an additional 115.9 parts by weight of methyl isoamyl ketone. The reaction was heated to 80� and held at that temperature of about two hours. Finally, 148.3 parts by weight of isobutyl alcohol was added.
A mixture of 333 parts by weight of isophorone diisocyanate, 300 parts by weight of methyl isoamyl ketone, and 0.5 parts by weight of dibutyl tin dilaurate was charged to a suitable reaction vessel under an inert atmosphere. An addition of 109.7 parts by weight of 2-ethyl-1,3-hexanediol was made to the flask. During the addition, the temperature was kept below 40� C.. Next, 20 parts by weight of methyl isoamyl ketone was added. The temperature of the reaction mixture was increased to 50� C. followed by addition of 192.9 parts by weight of beta-hydroxy butyl carbamate and an addition 421 parts by weight of methyl isoamyl ketone. The reaction mixture was slowly increased to 90� C. and 40 parts by weight of isobutanol were added. The reaction mixture was held at 90� C. until all of the isocyanate functionality had reacted.
An acrylic resin having cyclic carbonate functionality (from copolymerization of the cyclic carbonate of glycidyl methacrylate) and a theoretical Tg of -39� C. (as determined from the Fox equation) was reacted with an excess of ammonium hydroxide. Following completion of the reaction, as determined by infrared analysis, the reaction mixture was vacuum stripped to a measured 96.7% nonvolatile content. The resulting product of a beta-hydroxy carbamate-functional acrylic had a theoretical carbamate equivalent weight of 723 grams per equivalent.
An acrylic resin was prepared with a theoretical Tg of -24, hydroxyl equivalent weight of 365 grams/equivalent, and a weight average molecular weight of 3858.
A mixture of 532.9 parts by weight methyl isoamyl ketone, 597.2 parts by weight of hexamethylene diisocyanate, and 0.8 parts by weight of dibutyl tin dilaurate were heated to 31� C. under an inert atmosphere. Keeping the temperature below 71� C., 259.8 parts by weight of 2-ethyl-1,3-hexanediol were then added over about 30 minutes. Following the addition, the reaction mixture was heated to 80� C. and held at that temperature for about 70 minutes. An addition of 862.3 parts of T-1890/100 (an isocyanurate available from CreaNova) was made to the reaction mixture. After the T-1890/100 was in solution, 944.3 parts by weight of beta-hydroxy butyl carbamate was added over about 17 minutes, holding the temperature of the reaction mixture below 92� C.. An additional 106.6 parts of methyl isoamyl ketone was added and the reaction mixture held at 90� C until all of the iso cyanate functionality was consumed. Then 264.6 parts by weight of isobutanol were added.
A clearcoat coating composition was prepared by mixing together 163.2 parts by weight of the product of Preparation 5, 29.4 parts by weight of the resin of Preparation 3, 40.9 parts by weight of Resimene� 747 (a hexamethoxymethyl melamine available from Solutia Inc., Springfield Mass.), 6.3 parts by weight of a UVA solution, 3.0 parts by weight of a hindered amine light stabilizer, 1.6 parts by weight of a rheology control agent, 12.0 parts by weight of a blocked sulfonic acid catalyst (25% active by weight), 10.0 parts by weight of n-butanol, 14.0 parts by weight of Exxate 600 (an oxo-hexyl acetate available from Exxon Chemical Co.), and 120.8 parts by weight of methyl isoamyl ketone. The measured nonvolatile content for the composition was 51%NV by weight. The composition produced a continuous film when sprayed over a black basecoat on a test panel.
A clearcoat coating composition was prepared by mixing together 195.2 parts by weight of the product of Preparation 1, 29.6 parts by weight of the resin of Preparation 3, 39.7 parts by weight of Resimene� 747 (a hexamethoxymethyl melamine available from Solutia Inc., Springfield Mass.), 6.3 grams of a UVA solution (95% nonvolatile by weight), 3.0 parts by weight of a hindered amine light stabilizer, 1.6 parts by weight of a rheology control agent (12.5% nonvolatile by weight), 12.0 parts by weight of a blocked sulfonic acid catalyst (25% active by weight), 10.0 parts by weight of n-butanol, 14.0 parts by weight of Exxate 600 (an oxo-hexyl acetate available from Exxon Chemical Co.), and 89.8 parts by weight of methyl isoamyl ketone. The measured nonvolatile content for the composition was 51.7%NV by weight.
A clearcoat coating composition was prepared by mixing together 101.9 parts by weight of the product of Preparation 5, 20.5 parts by weight of Resimene� 747 (a hexamethoxymethyl melamine available from Solutia Inc., Springfield Mass.), 3.2 parts by weight of a UVA solution (95% nonvolatile by weight), 1.5 parts by weight of a hindered amine light stabilizer, 0.8 parts by weight of a rheology control agent (12.5% nonvolatile by weight), 6.0 parts by weight of a blocked sulfonic acid catalyst (25% active by weight), 0.02 parts by weight of n-butanol, 0.55 parts by weight of Exxate 600 (an oxo-hexyl acetate available from Exxon Chemical Co.), and 14.8 parts by weight of methyl isoamyl ketone. The composition did not produce a continuous film.
A clearcoat coating composition was prepared by mixing together 99.9 parts by weight of the product of Preparation 2, 14.6 parts by weight of Resimene� 747 (a hexamethoxymethyl melamine available from Solutia Inc., Springfield Mass.), 2.6 parts by weight of a UVA solution (95% nonvolatile by weight), 1.2 parts by weight of a hindered amine light stabilizer, 0.6 parts by weight of a rheology control agent (12.5% nonvolatile by weight), 4.9 parts by weight of a blocked sulfonic acid catalyst (25% active by weight), 0.02 parts by weight of n-butanol, and 0.45 parts by weight of Exxate 600 (an oxo-hexyl acetate available from Exxon Chemical Co.). The composition did not produce a continuous film.
A clearcoat coating composition was prepared by mixing together 123.1 parts by weight of the product of Preparation 1, 19.8 parts by weight of Resimene� 747 (a hexamethoxymethyl melamine available from Solutia Inc., Springfield Mass.), 3.2 parts by weight of a UVA solution (95% nonvolatile by weight), 1.5 parts by weight of a hindered amine light stabilizer, 0.8 parts by weight of a rheology control agent (12.5% nonvolatile by weight), 6.0 parts by weight of a blocked sulfonic acid catalyst (25% active by weight), 0.02 parts by weight of n-butanol, 0.55 parts by weight of Exxate 600 (an oxo-hexyl acetate available from Exxon Chemical Co.), and 14.8 parts by weight of methyl isoamyl ketone. The composition did not produce a continuous film.
Clearcoat coating compositions were prepared by mixing together ingredients as shown in the following table.
______________________________________Ingredient  Example 3   Example 4                            Compar. Ex. D______________________________________Preparation 4       141.3       185.6    206.3resinPreparation 1       151.2       50.4     --resinResimene � 747       30.9        30.9     30.9Catalyst    8.0         8.0      8.0Adhesion    4.8         4.8      4.8additiveRheology    32.3        32.3     32.3control agentsLight       31.7        31.7     31.7stabilizeradditivesFlow additive       2.0         2.0      2.0Exxate 600  3.24        19.2     33.2Methyl isoamyl       --          16.0     30.0ketone______________________________________
Testing of Coating Compositions of Examples 3 and 4 and Comparative Example D
Primed plastic panels were coated with a black basecoat and then the clearcoat composition wet-on-wet. The coated panels were cured after application of the clearcoat composition by baking at 120� C. for 30 minutes in a gas-fired oven. The cured clear coat films were 1.5-2.0 mils thick.
______________________________________ClearcoatComposition     Etch Rating______________________________________Example 3       6Example 4       4Comparative Ex. D           9______________________________________
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS5872195 *Jul 1, 1997Feb 16, 1999Basf CorporationCurable coating compositions containing carbamate additive* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS6780909 *Apr 10, 2001Aug 24, 2004Basf CorporationCoating composition having low volatile organic contentUS6844395Dec 12, 2002Jan 18, 2005Basf CorporationAsymmetric diisocyanate monomers in urethane polymers and oligomers to reduce crystallinityUS6995208Dec 11, 2001Feb 7, 2006Basf CorporationClearcoat composition for primerless MVSS adhesionUS7138463Dec 3, 2004Nov 21, 2006Basf CorporationCarbamate functional addition polymers and a method for their preparationUS7160973Dec 12, 2002Jan 9, 2007Basf CorporationUrethane polymers that reduce the effect of polylactone linkagesUS7179861Apr 1, 2004Feb 20, 2007Basf CorporationCarbamate functional addition polymers and a method for their preparationUS7232863Oct 1, 2004Jun 19, 2007Basf Corporationungelled polymers made by reacting a linear unsaturated anhydride compound, an active hydrogen compound, and an epoxide compound under specified conditions; made without using transcarbamylation; thermoset clear coats for the exteriors of automotive vehiclesUS7297749Oct 14, 2004Nov 20, 2007Basf CorporationAsymmetric polyisocyanate monomers in urethane polymers and oligomers to reduce crystallinityUS7342071Sep 15, 2005Mar 11, 2008Basf CorporationClearcoat paint compositionUS8278390Mar 23, 2007Oct 2, 2012Dow Corning CorporationCoatings with carbinol-functional siloxane resinEP1541639A1Nov 23, 2004Jun 15, 2005Basf CorporationUse of urea crystals for non-polymeric coatingsWO2007112094A2Mar 23, 2007Oct 4, 2007Dow CorningCoatings with carbinol- functional siloxane resinWO2008022922A1 *Aug 8, 2007Feb 28, 2008Basf AgNovel coating materials* Cited by examinerClassifications U.S. Classification525/481, 525/144, 525/514, 525/528, 525/129, 525/488, 525/146, 525/163, 525/510International ClassificationC09D133/00, C08G18/80, C08G81/02, C08K5/3492, C08G18/08, C09D169/00, C08G18/30, C09D175/00, C09D167/00, C07D251/34, C09D133/06, C08G18/10, C09D175/04, C08G18/66, C08G59/14, C08G18/28, C08G71/00, C08F8/30, C08G12/40, C08L61/20, C09D201/06, C09D201/02, C09D167/04, C09D161/20, C08G18/38, C08G18/46, C09D175/02Cooperative ClassificationC08G18/3829, C09D169/00, C09D201/025, C08G18/8077, C08G81/021, C08G12/40, C09D161/20, C08G59/1494, C08G18/2865, C09D201/02, C08F8/30, C09D133/06, C08K5/34924, C08G59/1438, C08G18/302, C08G18/3853, C08G18/3831, C08G18/10, C09D167/04, C09D175/00, C08G71/00, C09D133/062, C08G18/0823, C08G18/4615, C09D175/04, C09D201/06, C07D251/34, C08L61/20, C09D175/02, C08G59/1477, C09D167/00, C08G18/6633European ClassificationC08G18/10, C09D167/00, C09D133/06B, C09D175/04, C09D133/06, C09D175/02, C08K5/3492D, C08G59/14K2, C09D201/02, C08G18/28D6H, C08G18/08B6C, C08G59/14K4, C07D251/34, C08G12/40, C08F8/30, C08G71/00, C08G18/38F5D, C08G59/14S, C08G81/02D, C09D167/04, C09D175/00, C09D161/20, C08G18/80H4F, C08G18/46F, C09D201/02N, C08G18/30D, C09D201/06, C08G18/66M, C08G18/38F5F, C08G18/38F20N5, C09D169/00Legal EventsDateCodeEventDescriptionJun 5, 2012FPAYFee paymentYear of fee payment: 12Jun 12, 2008FPAYFee paymentYear of fee payment: 8Jun 14, 2004FPAYFee paymentYear of fee payment: 4Dec 11, 1998ASAssignmentOwner name: BASF CORPORATION, MICHIGANFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:OHRBOM, WALTER H.;MENOVCIK, GREGORY G.;ST. AUBIN, DONALDL.;AND OTHERS;REEL/FRAME:009636/0987;SIGNING DATES FROM 19981106 TO 19981202RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services