EP1838749A1 - Coating compositions containing rheology control agents - Google Patents
Coating compositions containing rheology control agentsInfo
- Publication number
- EP1838749A1 EP1838749A1 EP06718600A EP06718600A EP1838749A1 EP 1838749 A1 EP1838749 A1 EP 1838749A1 EP 06718600 A EP06718600 A EP 06718600A EP 06718600 A EP06718600 A EP 06718600A EP 1838749 A1 EP1838749 A1 EP 1838749A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rheology control
- coating composition
- control agent
- branched
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/771—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/04—Thixotropic paints
Definitions
- This invention relates to solvent-borne and water-borne coating compositions useful for finishing the exterior of automobiles and trucks, and in particular to coating compositions containing rheology control agents that provide the composition with improved rheology control to facilitate a spray application that provides a high quality automotive finish. DESCRIPTION OF THE PRIOR ART
- the finish of choice currently being used on automobiles and trucks is a clear coat/color coat finish in which a clear coating is applied over the pigmented color coat or base coat to provide protection to the color coat and improve the appearance of the overall finish particularly, gloss and DOI (distinctness of image).
- Mono-coats of pigmented finishes are also used without a clear coat on some automobiles and trucks, in particular, older models.
- Primers, primer-surfacers, and sealers for many automotive and truck applications are applied initially before one of the aforementioned top coats are applied. All of the above compositions when applied by conventional spraying techniques, have rheology control problems, such as, running and sagging after application.
- Top coat finishes containing flake pigments or special effect pigments have problems with flake control and proper flake orientation for optimum appearance. Additional problems are caused by many localities having regulations requiring the use of low VOC (volatile organic content) coating compositions to reduce air pollution. Typically, these low VOC coating compositions have a VOC of 2.1 pounds/gallon (252 g/l) or less and when applied by conventional spray techniques often have problems with running and sagging of the finish after application and also problems with proper flake orientation and control.
- VOC volatile organic content
- low VOC coating compositions typically are used for OEM, refinishing or repainting of automobiles and trucks or parts thereof and are usually formulated using relatively low molecular weight polymers.
- such compositions generally have poor rheology control and run and sag after spray application particularly when applied to vertical surfaces, such as, door panels and body side panels and have poor flake orientation and flake control.
- a rheology control agent is needed to form a coating composition having improved rheology control that prevent runs and sags after application and in general provides a finish with an acceptable appearance with good gloss and DOI.
- Rheology control is also very critical for the low solids lacquer basecoats typically used in the refinishing or repainting of automobiles and trucks.
- These lacquer basecoats are typically applied at very low solids, as low as 10 percent by volume, using spray application. To achieve adequate hiding in these coatings, a dry film thickness of around 15 to 65 microns is typically required. Because of the very low volume solids of these coatings, the applied wet film thickness of these coatings can be around 350 microns or more. This requires the use of a very effective rheology control agent to prevent sagging and to give good flake orientation.
- Another aspect of these lacquer coatings is that they typically contain higher molecular weight binder components which can be incompatible with many conventional rheology control agents.
- Rheology control agents are shown in U.S. Patent 3,893,956, U.S. Patent 4,311 ,622, U.S. Patent 4,314,924, U.S. Patent 4,677,028, U.S. Patent 4,851 ,294, U.S. Patent 6,420,466 B1 , U.S. Patent 6,617,468 B2, and EP 0683214, EP 1162242, DE 10241853 B3 and WO 03037849.
- These rheology control agents of the prior art in general cannot be formulated into high solids compositions and do not provide the necessary level of optical clarity to the resulting finishes and form finishes having low DOI levels, particularly when the coating compositions are ambient temperature curing compositions.
- Some of these rheology control agents have to be prepared in the presence of the binder of the coating composition to achieve the desired level of rheology control, which adds to the manufacturing costs of the composition by requiring additional manufacturing steps and the use of specific and also expensive equipment.
- Some rheology control agents for example, taught by U.S. 6,617,468 B2 limit the weatherability of the resulting finish, which over time negatively impacts the appearance of the finish.
- Some rheology control agents for example, taught by U.S. 4,311,622 are limited in their compatibility with the resin system. These rheology control agents are based on a symmetrical structure.
- some rheology control agents for example, taught by U.S. 4,311 ,622 or WO 02064684 show insufficient compatibility in the resin system of choice especially rheology control agents prepared using hydroxyl functional monoamines.
- the present invention is directed towards coating compositions comprising a liquid carrier and film forming binder and a rheology control agent having improved rheology control in both high and low solids solvent-borne and water-borne coating compositions useful for OEM and refinishing or repainting the exterior of automobile and truck bodies and parts thereof.
- the rheology control agent used in the coating composition of this invention comprises the following compound represented by the following formula including isomers and mixtures of isomers thereof:
- Substrates having adhered thereto a layer of the novel coating composition containing the rheology control agent and the novel rheology control agent are also part of this invention.
- the coating compositions of this invention containing the novel rheology control agent are solvent-borne or water-borne coating compositions and in particular are clear and pigmented paint compositions used for OEM, refinishing or repainting the exterior of automobiles and trucks.
- the rheology control agent improves and controls the rheology of the coating compositions to facilitate spray applications and provide a Class A automotive finish having an excellent overall appearance and good DOI.
- the resulting finish does not sag or run particularly when spray applied to vertical surfaces. Under high shear conditions such as occur when the coating composition is applied, for example, by spraying, the viscosity of the composition is significantly reduced.
- the shear conditions are low and the viscosity increases significantly to eliminate runs and sags on a vertical surface and provides a finish with an excellent appearance. Also, proper orientation of flake or special effects pigments that are used in base coats and mono-coats is controlled and the pigment and flake settling properties of such coatings are also improved.
- the coating compositions of this invention can also be used as primer, primer surfacers, and primer fillers.
- a compound which can provide rheology control to a coating composition must be compatible with the coating composition and not deteriorate the properties of the resulting finish, such as, gloss and DOI or the weatherability or durability of the finish. Small changes in the chemical composition of a compound can significantly affect its use as a rheology control agent.
- Rheological measurements are useful in characterizing the effectiveness of a rheology control agent, but the final measure of the ability of a compound to provide effective rheology control in a coating composition, is to test the compound in a coating composition using conventional application conditions, such as, spray application, optionally, with subsequent drying or baking of the resulting finish and observe the resulting appearance of the finish.
- solvent-borne or water-borne coating compositions containing the novel rheology control agent comprise 5 to 95 percent by weight solvent or an aqueous carrier, based on the weight of the coating composition, and 5 to 95 percent by weight of binder, which includes the rheology control agent, also based on the weight of the coating composition.
- the level of rheology control agent in such coating compositions is in the range of 0.1 to 30 percent by weight, based on the weight of the binder, and preferably, 0.1 to 10 percent by weight based on the weight of the binder.
- the coating compositions can be 100 percent binder solids compositions and the rheology control agents are used in the ranges shown above.
- binder refers to the film forming constituents of the composition and includes any crosslinking components, such as, polyisocyanates, optional polymeric and/or oligomeric components, and optional reactive diluents. Solvents, pigments, catalysts, antioxidants, U.V. absorbers, light stabilizers, leveling agents, antifoaming agents, anti-cratering agents and adhesion promoting agents are not included in the term.
- Tg glass transition temperature
- “Lacquer” is a coating composition, which dries via evaporation of the carrier, such as, a solvent, water or a mixture of solvent and water without any substantial crosslinking of the binder of the coating composition.
- the rheology control agent used in the coating composition of this invention is a compound having following formula
- A, B, C and D equal CH 2 , CHR, NH, or O, and A, B, C and D may be the same or different and at least one of A and B equals NH and at least one of C and D equals NH; and wherein R-i, R 2 , and R 3 may be the same or different and represent a linear, branched, hyper-branched, or dendritic ether, polyether or hydrocarbon based chain, optionally forming at least one carbon-based ring, being saturated or unsaturated and R 2 represents linear or branched alkylenes, ethers, polyethers, or polyester linkages and at least one of Ri, R 2 , and R 3 comprises an ester group which is branched off from the main chain.
- Novel rheology control agents of this invention comprise the above Formula (1) having the various constituents defined as above with the exception that excluded from Formula (1) is a compound wherein R 2 is CH 2 -CH 2 -CH 2 -CH 2 -CH(C(O)OCH 3 ), A, B, C and D are NH and R 1 and R 3 are both equal to a linear octyl hydrocarbon chain.
- rheology control agents used in solvent-borne coatings, water-borne coatings or 100 percent solids coatings of this invention that provide the coating compositions with excellent rheology control on application and form finishes that have excellent overall appearance, good DOI, do not sag or run on application, and have good flake orientation.
- these rheology control agents can be used in conjunction with a wide variety of coating compositions containing as the binder, polyacrylates, linear poly(meth)acrylates, branched, grafted or segmented poly(meth) acrylates.acrylic alkyd resins, polyesters, branched copolyesters, carbamates, oligomers or polyesterurethanes.
- These coating compositions may also utilize crosslinking agents, such as, polyisocyanates, alkylated melamines, melamine derivatives, and epoxides and other crosslinking agents.
- crosslinking agents such as, polyisocyanates, alkylated melamines, melamine derivatives, and epoxides and other crosslinking agents.
- R 2 comprises an ester group which is branched off from the main chain of the molecule.
- Specific examples of this embodiment include, but are not limited to the following structures:
- A, B, C and D are NH
- R 2 comprises an ester group which is branched off from the main chain of the molecule
- R ⁇ and R 3 each comprises at least one ester group.
- Specific examples of this embodiment include, but are not limited to the following structures:
- A, B, C and D are NH and R 2 comprises an ester group which is branched off from the main chain of the molecule, and Ri and R3 each comprises at least one urethane group.
- R 2 comprises an ester group which is branched off from the main chain of the molecule
- Ri and R3 each comprises at least one urethane group.
- R 2 comprises an ester group which is branched off from the main chain of the molecule
- Ri and R3 comprise at least one urea group. Specific examples of this embodiment include, but are not limited to the following structures:
- R 2 comprises at least one ester group which is branched off the main chain.
- Specific examples of this embodiment include, but are not limited to the following structures:
- Ri and R 3 each comprises at least one urea group and one ester group which is branched off from the main chain of the molecule.
- Specific examples of this embodiment include, but are not limited to the following structure:
- the rheology control agents shown in Formulas 2 to 34 are novel compounds.
- the branched rheology control agents of this invention may be formed using a variety of synthetic methods. Synthesis of structures (2- 16, 23-31) for example, may comprise reacting an amine with a diisocyanate in a suitable reaction vessel generally at a temperature between O 0 C and 120 0 C, preferably, from 1O 0 C to 8O 0 C and optionally, in the presence of a diluent.
- the synthesis of the branched rheology control agent of this invention comprises adding a solution of an organic diisocyanate in a dry solvent, such as chloroform, under an inert atmosphere, such as nitrogen, to a solution of a corresponding amino acid ester typically in a 1 :2 molar ratio.
- a dry solvent such as chloroform
- an inert atmosphere such as nitrogen
- the resulting reaction mixture is held under relatively cold conditions, such as 10 0 C, and then after addition of the diisocyanate solution the reaction mixture is allowed to warm and to continue, for example, about 1-3 hours with agitation or until the IR (infra red) isocyanate peak (about 2258 cm "1 ) disappears as monitored by an IR spectrophotometer.
- the rheology control agent that was formed is isolated, for example, by conventional techniques, like filtration or evaporation of solvent and the agent is washed with appropriate solvent and dried, for example, in a vacuum at room temperature.
- structures 2-16 and 23-31 may be obtained by reacting an isocyanate with a diamine in a suitable reaction vessel, generally at a temperature between O 0 C and 12O 0 C, preferably, from 10°C to 8O 0 C and optionally, in the presence of a diluent.
- Suitable amines or diamines for the formation of subject invention include, but are not limited to, 2-amino-4-methylpentanoate alkyl ester, aminoethanoate alkyl ester, 2-amino-3-phenylpropanoate alkyl ester, 2- aminopropanoate alkyl ester, 2-amino-3-carbamoylpropanoate alkyl ester, diethyl 2-aminobutanedioate alkyl ester, 2-amino-4-carbamoylbutanoate alkyl ester, 2-aminopentanedioate alkyl ester, 2-amino-3- methylpentanoate alkyl ester, 2-amino-4-(methylthio)butanoate ester, 2- amino-3-hydroxypropanoate alkyl ester, 2-amino-3-hydroxybutanoate alkyl ester, 2-amino-3-(4-hydroxyphenyl)-propanoate al
- Suitable isocyanates or diisocyanates for the formation of subject invention include, but are not limited to, hexamethylene diisocyanate, 1 ,4- diisocyanatobutane, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, 4,4'-diphenyl methane diisocyanate, 2,2'-diphenyl methane diisocyanate, 2,4'-diphenyl methane diisocyanate, isophorone diisocyanate, m- tetramethylxylene diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, naphthalene 1 ,5-diisocyanate, p-phenylene diisocynate, methyl 2,6- diisocyanatohexanoate, octyl isocyanate, cyclohexyl isocyanate, but
- branched rheology control agents (17, 18, 19, 21 , and 22) of this invention may be formally separated into several steps. These steps may be carried out sequentially in one reaction vessel or in different reaction vessels followed by separation and/or purification steps.
- Certain rheology control agents (21 and 22) of this invention may be formed by first reacting an amino alcohol component with a mono- isocyanate component. This intermediate is further reacted with a diisocyanate component to form the rheology control agent.
- the other rheology control agents (17, 18 and 19) are formed by first reacting an amino alcohol component with a diisocyanate component. The reaction temperature and reactant concentration is selected to favor the formation of the intermediate addition product.
- Suitable aminoalcohols for the formation of subject invention include but are not limited to 2-amino-2-(hydroxyethyl)propane-1 ,3-diol, 1 ,3-diamino-2-hydroxypropane, 2-hydroxyethylamine, 3- hydroxypropylamine, or mixtures thereof.
- Suitable mono-isocyanates or diisocyanates for the formation of subject invention include but are not limited to, methyl 2,6- diisocyanatohexanoate, octyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, hexyl isocyanate, undecyle isocyanate, or mixtures thereof.
- the branched rheology control agents of this invention may be formed using a variety of synthetic methods.
- Synthesis of structure (20) may comprise reacting a diisocyanate with an alcohol in the presence of a urethane catalyst such as dibutyl tin dilaurate at a temperature from 25°C to 12O 0 C, preferably from 40 0 C to 90 0 C.
- a urethane catalyst such as dibutyl tin dilaurate
- Suitable diisocyanates include but are not limited to methyl 2,6- diisocyanatohexanoate.
- Suitable alcohol include but are not limited to butanol, hexanol, octanol, decyl alcohol, undecyl alcohol, monomethyl ether polyethylene glycol, and mixtures thereof.
- branched rheology control agents (32 & 33) of this invention may be formally separated into several steps. These steps may be carried out sequentially in one reaction vessel or in different reaction vessels followed by separation and/or purification steps.
- Certain rheology control agents (32 & 33) of this invention may be formed by first reacting an amino acid ester with a mono-isocyanate component at 1:1 molar ratio in a dry solvent. This intermediate is further reacted with another or the same mono-isocyanate component to form the rheology control agent.
- Suitable amino acid ester for the formation of subject invention include but are not limited to 3-hydroxy- aspartic acid dimethyl ester, serine benzylester, serine t-butylester, serine ethylester, serine methylester, serine isopropyl ester, ⁇ -hydroxy-phenylalanine methyl ester, threonine methyl ester, or mixtures thereof.
- Suitable mono-isocyanates for the formation of subject invention include but are not limited to, octyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, hexyl isocyanate, undecyle isocyanate, decyle isocyanate, or mixtures thereof.
- Suitable diisocyanates for the formation of subject invention include, but are not limited to, hexamethylene diisocyanate, 1,4- diisocyanatobutane, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, 4,4'-diphenyl methane diisocyanate, 2,2'-diphenyl methane diisocyanate, 2,4'-diphenyl methane diisocyanate, isophorone diisocyanate, m- tetramethylxylene diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, naphthalene 1 ,5-diisocyanate, p-phenylene diisocynate, methyl 2,6- diisocyanatohexanoate, or mixtures thereof.
- Rheology control agent (34) of this invention may be formally separated into several steps. These steps may be carried out sequentially in one reaction vessel or in different reaction vessels followed by separation and/or purification steps.
- Rheology control agent (34) of this invention may be formed by first reacting an amino acid ester with a mono-isocyanate component at 1:1 molar ratio in a dry solvent. This intermediate is further reacted with another diisocyanate component to form the rheology control agent at 2:1 molar ratio.
- the rheology control agent can be formulated, dissolved, or dispersed in an organic solvent or a mixture of solvents. More preferably, the solvent is a ketone, ester, acetate, blend of ester and alcohol, aprotic amide, aprotic sulfoxide, organic acid with a pKa less than 5.5, blend of organic acids with the above solvents or aprotic amine.
- the solvent is a ketone, ester, acetate, blend of ester and alcohol, aprotic amide, aprotic sulfoxide, organic acid with a pKa less than 5.5, blend of organic acids with the above solvents or aprotic amine.
- Examples of other useful solvents include methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, amyl acetate, ethylene glycol butyl ether acetate, propylene glycol monomethyl ether acetate, xylene, N-methylpyrrolidone, 1-ethyl-2- pyrrolidinone, 1 -(2-hydroxyethyl)-2-pyrrolidinone, 1 -cyclohexyl-2- pyrrolidone, 1-ethyl-2-pyrrolidinone, 1-vinyl-2-pyrrolidone, 2-pyrrolidone-5- carboxylic acid, 1 ,5-dimethyl-2-pyrrolidinone, 1-benzyl-2-pyrrolidinone, acetic acid, dodecylbenzene sulfonic acid, alkyl sufonic acids, aryl sulfonic acids, formic acid, phosphoric acid, blends of acidic
- the rheology control agent of this invention can be combined with the film forming coating system using a variety of methods.
- the rheology control agent can be added to the film forming coating mixture as a solid in powder form. Agitation methods, known to those skilled in the art, may be used to disperse, dissolve or distribute the rheology control agent.
- the use of a high speed disperser has been found to be a particularly effective dispersing technique at dispersing these rheology control agents in a binder component and solvent of the coating formulation. This dispersion is subsequently added to the other components of the coating formulation to make the final coating.
- the rheology control agent can be prepared directly using the binder system of the film forming coating mixture as the reaction medium using the general synthesis procedures outlined above.
- rheology control agents have been produced in the presence of a binder resin as shown, for example, in GB 1 ,454,414, wherein a urea adduct is prepared in situ in the presence of the binder.
- the rheology control agents of this invention may also be produced in the presence of a binder to directly form a desired fibril structure in the binder resin.
- the length of the fibrils can be adjusted as known to those skilled in the art using, for example, a shear treatment, or by modifying the mixing conditions.
- the rheology control agents of this invention may also be prepared following the outlined synthesis procedures directly from the starting materials described above by using a non-solvent, which has a limited solubility for the product.
- This strategy results in a precipitate that can be used as such, be milled in order to reduce the average length, or be re- crystallized, for example to increase the purity or to change the structural morphology or fibril length.
- the dosing conditions or the stirrer speed can be changed to influence the average structure build or fibril formation.
- the rheology control agents of this invention may also be utilized in the form of their solutions at temperatures between 0 and 15O 0 C and in a polar solvent optionally containing 0-3.0 mols of an inorganic or organic acid compounds per urea group.
- the rheology control agents of this invention as defined above have a solids content of 10 - 75 wt. % and preferably of 15 - 40 wt. %.
- Suitable solvents for this purpose are, for example, N-methyl pyrrolidone, dimethyl acetamide, n-butanol, aliphatic diols, butyl glycol, acetic acids, 1- ethyl-2- pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinone, 1-cyclohexyl-2- pyrrolidone, 1-ethyl-2-pyrrolidinone, 1-vinyl-2-pyrrolidone, 2-pyrrolidone-5- carboxylic acid, 1 ,5-dimethyl-2-pyrrolidinone, 1-benzyl-2-pyrrolidinone and mixtures thereof.
- inorganic or organic acid compounds can be added to maximize the solids content and stability of these solutions.
- stability is meant no significant precipitation or gelation upon aging either at room temperature or at elevated temperature (up to 50 0 C) storage.
- Preferred inorganic compounds used in these solutions are selected from LiCI, LiBr, NaCI, KCI, CaCI2, LiNO3, lithium acetate, lithium acetylacetonate, tetraalkylammonium phosphate, organophosphate, LiOC(O)Me or other Li- salts of carboxylic acids, sulfonic acids, benzoic acids or substituted benzoic acids, with LiCI as the preferred inorganic compound.
- Preferred organic acid compounds used in these solutions are selected from dodecylbenzene sulfonic acid in isopropanol, p-toluene sulfonic acids and trifluoromethane sulfonic acid.
- some of these rheology control agents can be dissolved at high solids (>10% by weight) in solvent without the use of these inorganic compounds or organic acids.
- the solvent-borne coating compositions and water-borne coating compositions of this invention containing rheology control agents are useful in a wide variety of applications, such as, clear coating compositions, base coating compositions, pigmented mono coating compositions, primer surfacers and primer fillers.
- Typical binders used in these compositions are acrylic polymers, such as, poly(meth)acrylates, meaning both polyacrylates and polymethacrylates, linear, branched, grafted, or segmented poly(meth)acrylates, polyacrylourethanes, polyesters, branched copolyesters, oligomers, e.g., urethane oligomers, polyester urethanes, polyepoxides and carbamate functional polymers.
- Typical crosslinking agents that may be used in these compositions are polyisocyanates, blocked polyisocyanates, melamine crosslinking agents, alkylated melamines, silanes, benzoguanamines and other crosslinking agents known to those skilled in the art.
- the acrylic polymers used to form coating compositions containing the novel rheology control agent of this invention may be random polymers or structured copolymers, such as, block or graft copolymers.
- Particularly useful structured copolymers are the branched acrylics with segmented arms as disclosed in U.S. Serial No.: 10/983,462 filed November 8, 2004 and U.S. Serial No. 10/983,875 filed November 8, 2004, both of which are incorporated herein by reference.
- a block copolymer used in the present invention may have an AB diblock structure, or ABA or ABC triblock structure, for example, Graft copolymers can be used in the present invention having a backbone segment and a side chain segment(s). Random copolymers that can be used have polymer segments randomly distributed in the polymer chain.
- Acrylic AB, ABA or ABC block copolymers can be prepared by using a stepwise polymerization process such as anionic, group transfer polymerization (GTP) taught in U.S. Patent No. 4,508,880, Webster et al., ""Living” polymers and process for their preparation”, atom transfer radical polymerization (ATRP) taught in U.S. Patent No. 6,462,125, White et al., and radical addition fragmentation transfer (RAFT) taught in U.S. Patent No. 6,271 ,340, Anderson, et al. "Method of controlling polymer molecular weight and structure". Polymers so produced have precisely controlled molecular weight, block sizes and very narrow molecular weight distributions.
- GTP group transfer polymerization
- ATRP atom transfer radical polymerization
- RAFT radical addition fragmentation transfer
- Aqueous coating compositions containing AB block copolymers as pigment dispersants disclosed in Houze et al. U.S. Pat. No. 6,204,319, which is hereby incorporated by reference, can utilize the novel rheology control agents of this invention.
- Graft copolymers may be prepared by a macromonomer approach using the special cobalt chain transfer (SCT) method reported in U.S. Patent, No. 6,472,463, Ma, the disclosure of which is herein incorporated by reference.
- SCT cobalt chain transfer
- Random copolymers can be prepared using conventional free radical polymerization techniques as described in U.S. Patent, No. 6,451,950, Ma. The disclosure of which is herein incorporated by reference.
- Typically useful acrylic polymers have a number average molecular weight of about 1 ,000 to 100,000, a Tg of 10 to 100°C and contain moieties, such as, hydroxyl, carboxyl, glycidyl and amino groups.
- acrylic polymers are known in the art and the following are typical examples of monomers used to form such polymers: linear alkyl (meth)acrylates having 1 to 12 carbon atoms in the alkyl group, cyclic or branched alkyl (meth)acrylates having 3 to 12 carbon atoms in the alkyl group including isobomyl (meth)acrylate, hydroxy alkyl (meth)acrylates having 1 to 4 carbon atoms in the alkyl group, glycidyl (meth)acrylate, hydroxy amino alkyl (meth)acrylates having 1 to 4 carbon atoms in the alkyl group, and the polymers can contain styrene, alpha methyl styrene, vinyl toluene, (meth)acrylonitrile (meth)acryl amides, (meth)acrylic acid, (meaning both acrylic acid and methacrylic acid) trimethoxysilylpropyl (meth)acrylate and the like.
- Examples of (meth)acrylic acid esters useful for forming these acrylic polymers are methyl acrylate, ethyl acrylate, isopropyl acrylate, tert.-butyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate and the corresponding methacrylates.
- Examples of (meth)acrylic acid esters with cyclic alcohols are cyclohexyl acrylate, trimethylcyclohexyl acrylate, 4-tert.-butylcyclohexyl acrylate, isobornyl acrylate and the corresponding methacrylates.
- Additional unsaturated monomers that do not contain additional functional groups useful for forming the acrylic polymers are, for example, vinyl ethers, such as, isobutyl vinyl ether and vinyl esters, such as, vinyl acetate, vinyl propionate, vinyl aromatic hydrocarbons, preferably those with 8 to 9 carbon atoms per molecule.
- vinyl ethers such as, isobutyl vinyl ether and vinyl esters, such as, vinyl acetate, vinyl propionate, vinyl aromatic hydrocarbons, preferably those with 8 to 9 carbon atoms per molecule.
- vinyl ethers such as, isobutyl vinyl ether
- vinyl esters such as, vinyl acetate, vinyl propionate, vinyl aromatic hydrocarbons, preferably those with 8 to 9 carbon atoms per molecule.
- vinyl ethers such as, isobutyl vinyl ether
- vinyl esters such as, vinyl acetate, vinyl propionate, vinyl aromatic hydrocarbons, preferably those with 8 to 9 carbon atoms per molecule.
- olefinically polyunsaturated monomers may also be used. These are monomers having at least 2 free-radically polymerizable double bonds per molecule. Examples of these are divinylbenzene, 1 ,4-butanediol diacrylate, 1 ,6-hexanedio! diacrylate, neopentyl glycol dimethacrylate, glycerol dimethacrylate.
- Hydroxy-functional (meth)acrylic polymers generally are formed by free-radical copolymerization using conventional processes well known to those skilled in the art, for example, bulk, solution or bead polymerization, in particular by free-radical solution polymerization using free-radical initiators.
- Suitable hydroxyl-functional unsaturated monomers that are used to introduce hydroxyl groups into the acrylic polymer are, for example, hydroxyalkyl esters of alpha, beta-olefinically unsaturated monocarboxylic acids with primary or secondary hydroxyl groups. These may, for example, comprise the hydroxyalkyl esters of acrylic acid, methacrylic acid, crotonic acid and/or isocrotonic acid. The hydroxyalkyl esters of (meth)acrylic acid are preferred.
- Suitable hydroxyalkyl esters of alpha, beta-olefinically unsaturated monocarboxylic acids with primary hydroxyl groups are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyamyl (meth)acrylate, hydroxyhexyl (meth)acrylate.
- suitable hydroxyalkyl esters with secondary hydroxyl groups are 2-hydroxypropyl (meth)acrylate, 2- hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate.
- hydroxy functional acrylic polymers having a hydroxy equivalent weight of 300 to 1300 and are polymers of hydroxy alkyl (meth)acrylates and one or more of the aforementioned monomers.
- the hydroxyl equivalent weight is the grams of resin per equivalent of hydroxyl groups.
- One particularly preferred hydroxy containing acrylic polymer contains 35 to 50 percent by weight styrene, 15 to 25 percent by weight ethylhexyl methacrylate and 15 to 20 percent by weight isobornyl methacrylate and 20 to 30 percent by weight hydroxyethyl methacrylate.
- Additional useful hydroxy-functional unsaturated monomers are reaction products of alpha, beta-unsaturated monocarboxylic acids with glycidyl esters of saturated monocarboxylic acids branched in alpha position, for example with glycidyl esters of saturated alpha- alkylalkanemonocarboxylic acids or alpha,alpha'- dialkylalkanemonocarboxylic acids.
- These preferably comprise the reaction products of (meth)acrylic acid with glycidyl esters of saturated alpha.alpha-dialkylalkanemonocarboxylic acids with 7 to 13 carbon atoms per molecule, particularly preferably with 9 to 11 carbon atoms per molecule.
- These reaction products may be formed before, during or after the copolymerization reaction.
- hydroxy-functional unsaturated monomers are reaction products of hydroxyalkyl (meth)acrylates with lactones.
- Hydroxyalkyl (meth)acrylates which may be used are, for example, those stated above.
- Suitable lactones are, for example, those that have 3 to 15 carbon atoms in the ring, wherein the rings may also comprise different substituents.
- Preferred lactones are gamma-butyrolactone, delta- valerolactone, epsilon-caprolactone, beta-hydroxy-beta-methyl-delta- valerolactone, lambda-laurolactone or mixtures thereof. Epsilon- caprolactone is particularly preferred.
- the reaction products preferably comprise those prepared from 1 mole of a hydroxyalkyl ester of an alpha.beta-unsaturated monocarboxylic acid and 1 to 5 moles, preferably on average 2 moles, of a lactone.
- the hydroxyl groups of the hydroxyalkyl esters may be modified with the lactone before, during or after the copolymerization reaction.
- Suitable unsaturated monomers that can be used to provide the acrylic polymer with carboxyl groups are, for example, olefinically unsaturated monocarboxylic acids, such as, for example, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid. Acrylic acid and methacrylic acid are preferably used.
- Suitable unsaturated monomers that can be used to provide the acrylic polymer with glycidyl groups are, for example, allyl glycidyl ether, 3,4-epoxy-1-vinylcyclohexane, epoxycyclohexyl (meth)acrylate, vinyl glycidyl ether and glycidyl (meth)acrylate. Glycidyl (meth)acrylate is preferably used.
- Free-radically polymerizable, olefinically unsaturated monomers which, apart from at least one olefinic double bond, do not contain additional functional groups that can be used to form the acrylic polymer are, for example, esters of unsaturated carboxylic acids with aliphatic monohydric branched or unbranched as well as cyclic alcohols with 1 to 20 carbon atoms.
- the unsaturated carboxylic acids which may be considered, are acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid. Esters of (meth)acrylic acid are preferred.
- the acrylic polymer can contain (meth)acrylamides.
- Typical examples of such acrylic polymers are polymers of (meth)acrylamide and alkyl (meth)acrylates, hydroxy alkyl (meth)acrylates, (meth)acrylic acid and or one of the aforementioned ethylenically unsaturated polymerizable monomers.
- Acrylic oligomers having a number average molecular weight of 300 to 3,000 of the aforementioned monomeric components also can be used as an optional polymeric component. Useful acrylic oligomers are disclosed in U.S. Serial No. 10/617,585 filed July 11 , 2003.
- these oligomers can have the one or more of the following groups that are reactive with isocyanate: hydroxyl, carboxyl, glycidyl, amine, aldimine, phosphoric acid and ketimine.
- Acrylourethanes also can be used to form the novel coating composition of this invention.
- Typical useful acrylourethanes are formed by reacting the aforementioned acrylic polymers with an organic polyisocyanate. Generally, an excess of the acrylic polymer is used so that the resulting acrylourethane has terminal acrylic segments having reactive groups as described above. These acrylourethanes can have reactive end groups and/or pendant groups such as hydroxyl, carboxyl, amine, glycidyl, amide, silane or mixtures of such groups.
- Useful organic polyisocyanates are described hereinafter as the crosslinking component but also can be used to form acrylourethanes useful in this invention.
- Typically useful acrylourethanes are disclosed in Stamegna et al. U.S. Patent 4,659,780, which is hereby incorporated by reference.
- Polyesters can also be used, such as, hydroxyl or carboxyl terminated or hydroxyl or carboxyl containing polyesters.
- the following are typically useful polyesters or ester oligomers: polyesters or oligomers of caprolactone diol and cyclohexane dimethylol, polyesters or oligomers of tris-hydroxy ethylisocyanurate and caprolactone, polyesters or oligomers of trimethylol propane, phthalic acid or anhydride and ethylene oxide, polyesters or oligomers of pentaerythritol, hexahydrophthalic anhydride and ethylene oxide, polyesters or oligomers of pentaerythritol, hexahydrophthalic anhydride and butylene oxide as disclosed in U.S. 6,221 ,484 B1.
- polyesters and oligomers can be reacted with an organic isocyanate to form polyesterurethane polymers and oligomers that can be used in the novel composition.
- One useful polyesterurethane that can used in the composition is formed by reacting an aliphatic polyisocyanate with an aliphatic or cycloaliphatic monohydric alcohol and subsequently reacting the resulting composition with a hydroxy functional aliphatic carboxylic acid until all of the isocyanate groups have been reacted.
- One useful polyurethane oligomer comprises the reaction product of the isocyanurate of hexane diisocyanate, cyclohexanol and dimethylol propionic acid.
- the branched copolyester polyol has a number average molecular weight not exceeding 30,000, alternately in the range of from 1 ,000 to 30,000, further alternately in the range of 2,000 to 20,000, and still further alternately in the range of 5,000 to 15,000.
- the copolyester polyol has hydroxyl groups ranging from 5 to 200 per polymer chain, preferably 6 to 70, and more preferably 10 to 50, and carboxyl groups ranging from 0 to 40 per chain, preferably 1 to 40, more preferably 1 to 20 and most preferably 1 to 10.
- the Tg (glass transition temperature) of the copolyester polyol ranges from -7O 0 C to 5O 0 C, preferably from - 65 0 C to 4O 0 C, and more preferably from -6O 0 C to 3O 0 C.
- the branched copolyester polyol is conventionally polymerized from a monomer mixture containing a chain extender selected from the group consisting of a hydroxy carboxylic acid, a lactone of a hydroxy carboxylic acid and a combination thereof; and one or more hyper branching monomers.
- the following additional ingredients can be included in the coating composition, particularly when the coating composition is useful as a lacquer, in amounts of 0.1% to 98% by weight and alternately in the range of 50% to 95% by weight, all based on the weight of the binder of the coating composition.
- Useful acrylic alkyd polymers having a weight average molecular weight ranging from 3,000 to 100,000 and a Tg ranging from O 0 C to 100 0 C are conventionally polymerized from a monomer mixture that can include one or more of the following monomers: an alkyl (meth)acrylate, for example, methyl (meth)acrylate, butyl (meth)acrylate, ethyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate; a hydroxy alkyl (meth)acrylate, for example, hydroxy ethyl (meth)acrylate, hydroxy propyl (meth)acrylate, hydroxy butyl (meth)acrylate; (meth)acrylic acid; styrene; and alkyl amino alkyl (meth)acrylate, for example, diethylamino ethyl (meth)acrylate or t-butyl aminoethyl methacrylate; and one or more of
- One preferred polymer is polymerized from a monomer mixture that contains an alkyl (meth)acrylate, hydroxy alkyl acrylate, alkylamino alkyl acrylate and vinyl oxazoline ester of drying oil fatty acids.
- Suitable iminiated acrylic polymers can be obtained by reacting acrylic polymers having carboxyl groups with an alkylene imine, such as propylene imine.
- Suitable cellulose acetate butyrates are supplied by Eastman Chemical Co., Kingsport, Tennessee under the trade names CAB-381-20 and CAB-531-1 and are preferably used in an amount of 0.1 to 20 percent by weight based on the weight of the binder.
- a suitable ethylene-vinyl acetate co-polymer is supplied by Honeywell Specialty Chemicals - Wax and Additives, Morristown, New Jersey, under the trade name A-C ® 405 (T) Ethylene - Vinyl Acetate Copolymer.
- Suitable nitrocellulose resins preferably have a viscosity of about 1/2-6 seconds.
- a blend of nitrocellulose resins is used.
- the lacquer can contain ester gum and castor oil.
- Suitable alkyd resins are the esterification products of a drying oil fatty acid, such as linseed oil and tall oil fatty acid, dehydrated castor oil, a polyhydric alcohol, a dicarboxylic acid and an aromatic monocarboxylic acid.
- Typical polyhydric alcohols that can be used to prepare the alkyd resin used in this invention are glycerine, pentaerythritol, trimethylol ethane, trimethylol propane; glycols, such as ethylene glycol, propylene glycol, butane diol and pentane diol.
- Typical dicarboxylic acids or anhydrides that can be used to prepare the alkyd resin are phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid maleic, and fumaric acid.
- Typical monocarboxylic aromatic acids are benzoic acid, paratertiary butylbenzoic acid, phenol acetic acid and triethyl benzoic acid.
- One preferred alkyd resin is a reaction product of an acrylic polymer and an alkyd resin.
- carbamate containing polymers are disclosed in U.S. Patent Application Publication 2003/0050388, which is hereby incorporated by reference and in particular discloses a carbamate polymer comprises the reaction product of an aliphatic polyisocyanate, a monohydric alcohol, a hydroxyfunctional aliphatic carboxylic acid and a polyalkylene ether glycol and has a number average molecular weight in the range of 100 to 2000.
- Other useful carbamate functional polymers are disclosed in Ramesh et al. U.S.
- Patent 6,462,144 B1 which is hereby incorporated by reference and shows a carbamate functional polymer having a hyperbranched or star polyol core, a first chain extension based on a polycarboxylic acid or anhydride, a second chain extension based on an epoxy containing compound, and having carbamate functional groups on the core, the second chain extension or both.
- Acrylic polymers having primary functional carbamate functionality are useful and are disclosed in U.S. Patent 5,866,259, which is hereby incorporated by reference.
- Suitable plasticizers include butyl benzyl phthalate, dibutyl phthalate, triphenyl phosphate, 2-ethylhexylbenzyl phthalate, dicyclohexyl phthalate, diallyl toluene phthalate, dibenzyl phthalate, butylcyclohexyl phthalate, mixed benzoic acid and fatty oil acid esters of pentaerythritol, poly(propylene adipate) dibenzoate, diethylene glycol dibenzoate, tetrabutylthiodisuccinate, butyl phthalyl butyl glycolate, acetyltributyl citrate, dibenzyl sebacate, tricresyl phosphate, toluene ethyl sulfonamide, the di-2-ethyl hexyl ester of hexamethylene diphthalate, and di(methyl cyclohexyl) phthalate
- the coating composition can include metallic driers, chelating agents, or a combination thereof.
- Suitable organometallic driers include cobalt naphthenate, copper naphthenate, lead tallate, calcium naphthenate, iron naphthenate, lithium naphthenate, lead naphthenate, nickel octoate, zirconium octoate, cobalt octoate, iron octoate, zinc octoate, and alkyl tin dilaurates, such as dibutyl tin dilaurate.
- Suitable chelating agents include aluminum monoisopropoxide monoversatate, aluminum (monoiospropyl)phthalate, aluminum diethoxyethoxide monoversatate, aluminum trisecondary butoxide, aluminum diisopropoxide monoacetacetic ester chelate and aluminum isopropoxide.
- polytrimethylene ether diols may be used as an additive having a number average molecular weight (Mn) in the range of from 500 to 5,000, alternately in the range of from 1,000 to 3,000; a polydispersity in the range of from 1.1 to 2.1 and a hydroxyl number in the range of from 20 to 200.
- Mn number average molecular weight
- the preferred polytrimethylene ether diol has a Tg of -75 0 C.
- Copolymers of polytrimethylene ether diols are also suitable.
- such copolymers are prepared by copolymerizing 1 ,3- propanediol with another diol, such as, ethane diol, hexane diol, 2-methyl- 1 ,3-propanediol, 2,2-dimethyl-1 ,3-propanediol, trimethylol propane and pentaerythritol, wherein at least 50 percent of the copolymer results from 1 ,3-propanediol.
- another diol such as, ethane diol, hexane diol, 2-methyl- 1 ,3-propanediol, 2,2-dimethyl-1 ,3-propanediol, trimethylol propane and pentaerythritol, wherein at least 50 percent of the copolymer results from 1 ,3-propanediol.
- a blend of a high and low molecular weight polytrimethylene ether diol can be used wherein the high molecular weight diol has an Mn ranging from 1 ,000 to 4,000 and the low molecular weight diol has an Mn ranging from 150 to 500.
- the average Mn of the diol should be in the range of 1 ,000 to 4,000.
- the polytrimethylene ether diols suitable for use in the present invention can include polytrimethylene ether triols and other higher functionality polytrimethylene ether polyols in an amount ranging from 1 to 20%, by weight, based on the weight of the polytrimethylene ether diol. It is believed that the presence of polytrimethylene ether diols in the crosslinked coating composition of this invention can improve the chip resistance of a coating resulting therefrom. Additional details of the foregoing additives are provided in U.S.
- Lacquer coating compositions can be formulated without the use of a crosslinking agent.
- Typical crosslinkable compositions that utilize the novel rheology control agents are solvent borne or water borne compositions having a binder containing in the range of 25-95 percent by weight of the aforementioned film forming polymer and 5-75 percent by weight of a crosslinking agent.
- the binder contains in the range of 40-90 percent by weight of the film forming polymer and 10-60 percent by weight of the crosslinking agent.
- Useful crosslinking agents include organic polyisocyanates, blocked organic polyisocyanates, melamines, alkylated melamines, benzoquanamines, epoxides and silanes
- Typical useful organic polyisocyanates crosslinking agents that can be used in the novel composition of this invention include aliphatic polyisocyanates, cycloaliphatic polyisocyanates and isocyanate adducts.
- Typical polyisocyanates can contain within the range of 2 to 10, preferably 2.5 to 8, more preferably 3 to 5 isocyanate functionalities.
- the ratio of equivalents of isocyanate functionalities on the polyisocyanate per equivalent of all of the functional groups present ranges from 0.5/1 to 3.0/1 , preferably from 0.7/1 to 1.8/1, more preferably from 0.8/1 to 1.3/1.
- Suitable aliphatic and cycloaliphatic polyisocyanates include the following: 4,4'dicyclohexyl methane diisocyanate, ("H 1 2MDI”), trans-cyclohexane-i ⁇ -diisocyanate, 1,6- hexamethylene diisocyanate (“HDI”), isophorone diisocyanate, ("IPDI”), other aliphatic or cycloaliphatic di-, tri- or tetra-isocyanates, such as, 1 ,2- propylene diisocyanate, tetramethylene diisocyanate, 2,3-butylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethyI hexamethylene diisocyanate, dodecamethylene diisocyanate, omega-dipropyl ether diisocyanate, 1 ,3-cyclopentane diisocyanate, 1 ,2 cyclo
- Tri-functional isocyanates also can be used, such as, Desmodur® N 3300, trimer of hexamethylene diisocyanate, Desmodur® 3400, trimer of isophorone diisocyanate, Desmodur® 4470 trimer of isophorone diisocyanate, these trimers are sold by Bayer Corporation.
- a trimer of hexamethylene diisocyanate sold as Tolonate® HDT from Rhodia Corporation is also suitable.
- An isocyanate functional adduct can be used, such as, an adduct of an aliphatic polyisocyanate and a polyol. Also, any of the aforementioned polyisocyanates can be used with a polyol to form an adduct.
- Polyols such as, trimethylol alkanes, particularly, trimethylol propane or ethane can be used to form an adduct.
- the melamine crosslinking agents are generally partially alkylated melamine formaldehyde compounds and may be monomeric or polymeric or mixtures thereof.
- suitable monomeric melamines include low molecular weight melamines which contain, on an average, three or more methylol groups etherized with a Ci to C 5 monohydric alcohol such as methanol, n-butanol, or isobutanol per triazine nucleus, and have an average degree of condensation up to about 2 and preferably in the range of about 1.1 to about 1.8, and have a proportion of mononuclear species not less than about 50 percent by weight.
- the polymeric melamines have an average degree of condensation of more than 1.9.
- suitable monomeric melamines include alkylated melamines, such as methylated, butylated, isobutylated melamines and mixtures thereof. Many of these suitable monomeric melamines are supplied commercially. For example, Cytec Industries Inc., West Patterson, New Jersey supplies Cymel ® 301 (degree of polymerization of 1.5, 95% methyl and 5% methylol), Cymel ® 350 (degree of polymerization of 1.6, 84 percent methyl and 16 percent methylol), 303, 325, 327 and 370, which are all monomeric melamines.
- Suitable polymeric melamines include high amino (partially alkylated) melamine known as Resimene ® BMP5503 (molecular weight 690, polydispersity of 1.98, 56 percent butyl, 44 percent amino), which is supplied by Solutia Inc., St. Louis, Missouri, or Cymel ® 1158 provided by Cytec Industries Inc., West Patterson, New Jersey. Cytec Industries Inc. also supplies Cymel ® 1130 @ 80 percent solids (degree of polymerization of 2.5), Cymel ® 1133 (48 percent methyl, 4 percent methylol and 48 percent butyl), both of which are polymeric melamines.
- appropriate catalysts may also be included in the activated compositions to accelerate the curing process of a potmix of the coating composition.
- the activated compositions include melamine as the crosslinking agent, it also preferably includes a catalytically active amount of one or more acid catalysts to further enhance the crosslinking of the components on curing.
- catalytically active amount of the acid catalyst in the coating composition ranges from about 0.1 percent to about 5 percent, preferably ranges from 0.1 percent to 2 percent, more preferably ranges from 0.5 percent to 1.2 percent, all in weight percent based on the weight of the binder.
- Some suitable acid catalysts include aromatic sulfonic acids, such as dodecylbenzene sulfonic acid, para- toluenesulfonic acid and dinonylnaphthalene sulfonic acid, all of which are either unblocked or blocked with an amine, such as dimethyl oxazolidine and 2-amino-2-methyl-1-propanol, n,n-dimethylethanolamine or a combination thereof.
- Other acid catalysts that can be used such as phosphoric acids, more particularly, phenyl acid phosphate, benzoic acid, oligomers having pendant acid groups, all of which may be unblocked or blocked with an amine.
- the coating composition preferably includes a catalytically active amount of one or more tin or tertiary amine catalysts for accelerating the curing process.
- catalytically active amount of the catalyst in the coating composition ranges from about 0.001 percent to about 5 percent, preferably ranges from 0.005 percent to 2 percent, more preferably ranges from 0.01 percent to 1 percent, all in weight percent based on the weight of the binder.
- catalysts can be used, such as, tin compounds, including dibutyl tin dilaurate and dibutyl tin diacetate; tertiary amines, such as, triethylenediamine.
- catalysts can be used alone or in conjunction with carboxylic acids, such as, acetic acid.
- carboxylic acids such as, acetic acid.
- the liquid carrier medium comprises an organic solvent or blend of solvents or an aqueous carrier comprising water and optionally, compatible organic solvents.
- the coating compositions contain about 5- 95 percent, more typically 10-85 percent by weight of solvent, and about 5-95 percent, more typically 15-90 percent by weight, of an organic liquid carrier (based on the weight of the coating composition).
- the selection of organic solvent depends upon the requirements of the specific end use application of the coating composition of this invention, such as the VOC emission requirements, the selected pigments, binder and crosslinking agents.
- organic solvents which are useful herein include alcohols, such as methanol, ethanol, n-propanol, and isopropanol; ketones, such as acetone, butanone, pentanone, hexanone, and methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone; alkyl esters of acetic, propionic, and butyric acids, such as ethyl acetate, butyl acetate, and amyl acetate; ethers, such as tetrahydrofuran, diethyl ether, and ethylene glycol and polyethylene glycol monoalkyl and dialkyl ethers, such as cellosolves and carbitols; and glycols, such as ethylene glycol and propylene glycol and mixtures thereof, and aromatic hydrocarbon solvents, such as xylene, toluene.
- alcohols such
- the novel coating composition may be used as a base coat or as a pigmented mono-coat topcoat. Both of these compositions require the presence of pigments. Typically, a pigment-to-binder ratio of 0.1/100 to 200/100 is used depending on the color and type of pigment used.
- the pigments are formulated into mill bases by conventional procedures, such as, grinding, sand milling, ball milling, high speed mixing, attritor grinding and two or three roll milling. Generally, the mill base comprises pigment and a dispersant in a liquid carrier. The mill base is added in an appropriate amount to the coating composition with mixing to form a pigmented coating composition.
- any of the conventionally-used organic and inorganic pigments such as, white pigments, like, titanium dioxide, color pigments, metallic flakes, such as, aluminum flake, special effects pigments, such as, coated mica flakes, coated aluminum flakes and the like, azo, anthraquinone, thioindigo, oxazine, quinacridone, lakes and toners of acidic dye stuffs, copper phthalocyanine and its derivatives, and various mixtures and modifications thereof and extender pigments can be used.
- the novel coating composition may be used as a primer, primer surfacer, or sealer in which case typical pigments used in primers would be added, such as, carbon black, barytes, silica, iron oxide and other pigments that are commonly used in primers in a pigment-to-binder ratio of 10/100 to 300/100.
- the coating composition formulated with the novel rheology control agent of this invention can be used as a clear coat that is applied over a pigmented base coat that may be a pigmented version of the composition of this invention or another type of a pigmented base coat.
- the clear coating can be in solution or in dispersion form.
- a clear coating is applied over the base coating before the base coating is fully cured. This is a so called "wet-on-wet process".
- a base coating is applied to a substrate and flash dried and then the clear coating is applied and both layers are then fully cured either at ambient temperatures or cured by heating to elevated temperatures, for example, of 50 0 C to 150°C for 15 to 45 minutes to form a clear coat/base coat finish.
- the primer or primer-surfacer is also flash dried and then the base coating and clear coating are applied as above. This is a so- called "wet on wet on wet" process.
- the base coating and clear coating preferably have a dry coating thickness ranging from 25 to 75 microns and 25 to 100 microns, respectively.
- the original OEM topcoat is usually sanded and a primer or sealer coat applied and then a mono coat or a basecoat/clear coat is applied.
- These coatings are usually cured at ambient temperatures or at slightly elevated temperatures, such as, 40 to 100 0 C.
- the novel coating composition contains about 0.1 to 5 percent by weight, based on the weight of the binder, of ultraviolet light absorbers.
- ultraviolet light absorbers include hydroxyphenyl benzotriazols, such as, 2- (2-hydroxy-5-methylpheny])-2H-benzotrazole, 2-(2-hydroxy-3,5-di- tert.amyl-phenyl)-2H-benzotriazole, 2[2-hydroxy-3,5-di(1 ,1- dimethylbenzyl)phenyl]-2H-benzotriazole, reaction product of 2-(2- hydroxy-3-tert.butyl-5-methyl propionate)-2H-benzotriazole and polyethylene ether glycol having a weight average molecular weight of 300, 2-(2-hydroxy-3-tert.butyl-5-iso-octyl propionate)-2H-benzotriazole; hydroxyphenyl s-triazines, such as, 2-[4-hydroxy-5-methylpheny]-2H-
- These clear coating compositions also may contain about 0.1 to 5 percent by weight, based on the weight of the binder, of a di- substituted phenol antioxidant or a hydroperoxide decomposer.
- a di- substituted phenol antioxidant or a hydroperoxide decomposer typically useful antioxidants include tetrakis[methylene(3,5-di-tert-butylhydroxy hydrocinnamate)]methane, octadecyl 3,5-di-tert-butyl-4- hydroxyhydrocinnamate, tris(2,4-di-tert-butylphenyl) phosphite, 1 ,3,5- tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1 ,3,5-triazine-2,4,6(1 H,3H,5H)-trione and benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C
- hydroperoxide decomposers include Sanko® HCA (9,10-dihydro-9-oxa-10-phosphenanthrene-10- oxide), triphenyl phosphate and other organo-phosphorous compounds, such as, Irgafos® TNPP from Ciba Specialty Chemicals, Irgafos® 168, from Ciba Specialty Chemicals, Ultranox® 626 from GE Specialty Chemicals, Mark PEP-6 from Asahi Denka, Mark HP-10 from Asahi Denka, Irgafos® P-EPQ from Ciba Specialty Chemicals, Ethanox 398 from Albemarle, Weston 618 from GE Specialty Chemicals, Irgafos® 12 from Ciba Specialty Chemicals, Irgafos® 38 from Ciba Specialty Chemicals, Ultranox® 641 from GE Specialty Chemicals and Doverphos® S-9228 from Dover Chemicals.
- These clear coating compositions also may contain about 0.1-5 percent by weight, based on the weight of the binder, of hindered amine light stabilizers.
- useful hindered amine light stabilizers include N- (1 ,2,2,6,6-pentamethyl-4-piperidinyl)-2-dodecyl succinimide, N(1acetyl- 2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecyl succinimide, N-
- coating composition utilizing the rheology control agent of this invention may contain a variety of other optional ingredients, including fillers, plasticizers, antioxidants, surfactants and flow control agents.
- the novel composition can contain 0.1 to 30 percent by weight, based on the weight of the binder, of acrylic NAD (non-aqueous dispersed) resins.
- These NAD resins typically are high molecular weight resins having a crosslinked acrylic core with a Tg between 20 to 100 0 C and attached to the core are low Tg stabilizer segments.
- a description of such NADs is found in Antonelli et al. U.S. Patent 4,591 ,533 and in Barsotti et al. U.S.
- these coating composition may include other conventional formulation additives known to those skilled in the art, such as, wetting agents, leveling and flow control agents, for example, Resiflow®S (polybutylacrylate), BYK® 320 and 325 (high molecular weight polyacrylates), BYK® 347 (polyether-modified siloxane), rheology control agents, such as, fumed silica, defoamers, surfactants and emulsifiers to help stabilize the composition.
- Other additives that tend to improve mar resistance can be added, such as, silsesquioxanes and other silicate- based micro-particles.
- One particularly useful additive is a blend of the novel rheology control agent and finely divided silica in a weight ratio of 0.1 :1 to 1 :0.1.
- Other particularly useful additive is a blend of the novel rheology control agent and bis-urea crystals as mentioned in U.S. 4,311 ,622 in a weight ratio of 0.1:1 to 1:0.1.
- the rheology control agent may be incorporated into one of the components of a typical two component (2K) coating composition.
- 2K two component
- the rheology control agent may be incorporated with the acrylic polymer component which is then blended with the isocyanate component just before application.
- Coating composition containing the novel rheology control agent can be applied by conventional techniques, such as, spraying, electrostatic spraying, dipping, brushing, and flow coating. Spraying and electrostatic spraying are preferred methods of application. In OEM applications, the composition is typically baked at 60°-
- the basecoat may be dried to a tack-free state and cured or preferably flash dried for a short period before the clear coat is applied (wet-on-wet).
- the base coat/clear coat finish is then baked as mentioned above to provide a dried and cured finish.
- the novel coating composition can also be formulated with the 3-wet (wet-on-wet-on-wet) coating process, where the primer, basecoat and clearcoat are applied in sequential steps without baking process in between each layer.
- the final coating is then baked to provide a dried and cure finish.
- the present invention is also applicable to non-baking refinish systems, as will be readily appreciated by those skilled in the art.
- the base coat may be allowed to "dry to the touch" at ambient temperature conditions or under warm air before the clear coating is applied.
- the base coating and clear coating preferably have a dry coating thickness ranging from 25 to 75 microns and 25 to 100 microns, respectively. These coatings are usually cured at ambient temperatures or at slightly elevated temperatures, such as, 40 to 100°C.
- the novel composition has uses for coating any and all items manufactured and painted by automobile sub-suppliers, frame rails, commercial trucks and truck bodies, including but not limited to beverage bottles, utility bodies, ready mix concrete delivery vehicle bodies, waste hauling vehicle bodies, and fire and emergency vehicle bodies, as well as any potential attachments or components to such truck bodies, buses, farm and construction equipment, truck caps and covers, commercial trailers, consumer trailers, recreational vehicles, including but not limited to, motor homes, campers, conversion vans, vans, large commercial aircraft and small pleasure aircraft, pleasure vehicles, such as, snow mobiles, all terrain vehicles, personal watercraft, motorcycles, and boats.
- the novel composition also can be used as a coating for industrial and commercial new construction and maintenance thereof; cement and wood floors; walls of commercial and residential structures, such as, office buildings and homes; amusement park equipment; concrete surfaces, such as parking lots and drive ways; asphalt and concrete road surface, wood substrates, marine surfaces; outdoor structures, such as bridges, towers; coil coating; railroad cars; printed circuit boards; machinery; OEM tools; signs; fiberglass structures; sporting goods; and sporting equipment.
- Example 3 The following reaction was carried out under a blanket of nitrogen.
- the reaction mixture was monitored with an IR spectrophotometer and when the isocyanate peak (about 2258 cm '1 ) disappeared the reaction was considered completed and the reaction mixture was filtered to remove the product formed and any residual solvent was removed under vacuum.
- the yield was 5.24 g, 87.3 percent yield.
- the resulting rheology control agent had the following formula:
- the reaction mixture was monitored with an IR spectrophotometer and when the isocyanate peak (about 2258 cm "1 ) disappeared the reaction was considered completed and the reaction mixture was filtered to remove the product formed and any residual solvent was removed under vacuum.
- the yield was 3.67 g, 73.7 percent yield.
- the resulting rheology control agent had the following formula:
- the reaction mixture was refluxed at 80 0 C for 2 hours with constant stirring.
- the reaction mixture was monitored with an IR spectrophotometer and when the isocyanate peak (about 2258 cm '1 ) disappeared the reaction was considered completed.
- the reaction mixture was precipitated out in water and filtered to remove the product formed and any residual solvent was removed under vacuum.
- the yield was 3.17 g, 63.4 percent yield.
- the resulting rheology control agent had the following formula:
- Example 12 The reaction was carried out under a blanket of nitrogen. 4.52 g
- Example 17 An acrylic or polyester based coating resin was combined with 2 percent of the rheology control agent and diluted with appropriate amount of solvent. After thorough mixing, the mixture was aged for at least one hour before viscosity was measured. The results on various rheology control agents are shown in Table 1. Table 1.
- Two aluminum paints were prepared by mixing the following ingredients (weight basis). The paint mixtures were sprayed onto primed steel panels. A clear composition of an acrylic urethane polymer was then sprayed over the aluminum paint on the panels and dried at ambient temperature for about 8 hours. Readings were taken on the panel with an absolute colorimeter described in U.S. Patent 4,412,744.
- a CAB Solution shown below, was produced by slowly adding cellulose acetate butyrate to solvent while mixing on an air mixer:
- a basecoat lacquer coating composition was made by adding the components listed in Table 2 in order on an air mixer:
- a random acrylic copolymer Sty/IBOMA/EHA/HEMA/BMA/MMA (10/10/15/30/10/25% by weight) at 66.40% wt solids in n-butyl acetate was prepared with the standard free radical polymerization procedure.
- Panel Preparation The silver basecoats were sprayed per the application instructions used for DuPont TM ChromaPremier® Basecoat specified in the DuPont ChromaSystem Tech Manual.
- the basecoats were sprayed to hiding over ACT APR10288 cold rolled steel panels which were wiped with DuPont First Klean 3900STM, sanded with 80 grit sand paper, wiped again with DuPont First Klean 3900STM, then primed with DuPontTM Variprime® 615STM/625STM Self-Etching Primer as per the instructions in the DuPont ChromaSystem Tech Manual.
- the basecoats were clearcoated with DuPontTM ChromaClear® V-7500STM Multi-Use as per the instructions in the DuPont ChromaSystem Tech Manual.
- Basecoat/clearcoat panels were flashed and then baked in a 140 0 F (6O 0 C) oven for 30 minutes. Topcoated panels were allowed to air dry for an additional 7 days prior to testing.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US64348205P | 2005-01-13 | 2005-01-13 | |
US64344005P | 2005-01-13 | 2005-01-13 | |
PCT/US2006/001547 WO2006076715A1 (en) | 2005-01-13 | 2006-01-13 | Coating compositions containing rheology control agents |
Publications (1)
Publication Number | Publication Date |
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EP1838749A1 true EP1838749A1 (en) | 2007-10-03 |
Family
ID=36121550
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP06718600A Withdrawn EP1838749A1 (en) | 2005-01-13 | 2006-01-13 | Coating compositions containing rheology control agents |
Country Status (4)
Country | Link |
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EP (1) | EP1838749A1 (en) |
CA (1) | CA2594735A1 (en) |
MX (1) | MX2007008503A (en) |
WO (1) | WO2006076715A1 (en) |
Families Citing this family (4)
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JP5752044B2 (en) | 2008-12-17 | 2015-07-22 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Quick-drying coating material |
EP3116926B1 (en) | 2014-03-12 | 2018-05-16 | Basf Se | Fast drying, hard elastic, scratch-proof and resistant coating compositions |
EP2808354A1 (en) | 2014-08-08 | 2014-12-03 | Basf Se | Fast drying, hard elastic, scratch-proof and resistant coating compositions |
US11760897B2 (en) | 2019-07-30 | 2023-09-19 | Axalta Coating Systems Ip Co., Llc | Coating compositions including a sag control agent and wax |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US6204319B1 (en) | 1998-10-30 | 2001-03-20 | E.I. Du Pont De Nemours And Company | Aqueous coating compositions |
US6362300B1 (en) * | 2000-07-06 | 2002-03-26 | The Yokohama Rubber Co., Ltd. | Moisture-curable polyurethane compositions |
SI1641888T1 (en) * | 2003-07-08 | 2012-06-29 | Nuplex Resins Bv | Amino acid derivatives and their use as a sag control agent |
-
2006
- 2006-01-13 EP EP06718600A patent/EP1838749A1/en not_active Withdrawn
- 2006-01-13 MX MX2007008503A patent/MX2007008503A/en unknown
- 2006-01-13 CA CA002594735A patent/CA2594735A1/en not_active Abandoned
- 2006-01-13 WO PCT/US2006/001547 patent/WO2006076715A1/en active Application Filing
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MX2007008503A (en) | 2007-09-04 |
CA2594735A1 (en) | 2006-07-20 |
WO2006076715A1 (en) | 2006-07-20 |
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