MXPA99003122A - Crosslinker compositions and low gloss epoxy coatings therefrom - Google Patents

Abstract

A novel crosslinker composition based on a combination of 1,3,5-tris-(2-carboxyethyl)isocyanurate and a dicarboxylic acid crosslinking agent is provided. Also provided is a curable epoxy composition employing, as the cross-linker component, a combination of 1,3,5-tris-(2-carbocyethly)isocyanurate and a dicarboxylic acid crosslinking agent, which curable composition finds use, for example, in coating applications. When cured, these coatings provide hard, durable and resistant films of low gloss.

Description

RETICULATING COMPOSITIONS AND LOW BRIGHTNESS EPOXY COATINGS THEREOF BACKGROUND OF THE INVENTION.

FIELD OF THE INVENTION The present invention generally discloses a carboxy-functional crosslinking composition comprising (i) 1,3-tris- (2-carboxyethyl) isocyanurate and / or a salt thereof, and (ii) a dicarboxylic acid crosslinking agent and / or a salt thereof. This invention also describes curable compositions which produce durable, low gloss over cure films. According to the present invention, the curable composition comprises in a broad concept, (i) a main resin component comprising a polyfunctional epoxy compound; and (2) a crosslinker component comprising carboxy functional gue (i) the crosslinker 1, 3, 5-tri- (2-carboxyethyl) isocyanurate and / or a salt of it, and (ii) a crosslinking agent of dicarboxylic acid and / or a salt of this.

DESCRIPTION OF PREVIOUS ART Coatings prepared by curing polyepoxides with acid cross-linking agents REF .: 29732 polybasic (including the salts thereof) have been described in numerous references, including US3730930, US3752870, US3781380, US3787521, US 4181642, US4346144, US4659718, US4681811, US4703101, US4764430, JP-A-61087767, JP-A-61087768 and JP-A-61087769, which at least are incorporated by reference even as if fully set forth. One of the most common such crosslinking agents of polybasic acid is 1,2-dodecanedioic acid. The coatings described in these references are mentioned as having certain advantageous characteristics such as for example image clarity, good adhesion and high gloss. US 5380804 (also incorporated by reference even as it is fully disclosed) discloses liquid and powder coatings which employ the 1, 3, 5-tris- (2-carboxyethyl) isocyanurate (hereinafter referred to as "TCI") as a cross-linking agent (carboxy-functional) of polybasic acid by main epoxy resins. Films derived from the described coatings are mentioned for possessing excellent hardness and strength properties as compared to films derived from commonly used carboxy-functional crosslinkers such as 1,2-dodecanedioic acid. Movies are also described as having high brightness.

Since strong and firm high-gloss films are preferred for certain uses, such as an automotive cover, a number of low-gloss applications for tough and firm films also exist. This could, therefore, be highly desirable, the low gloss having as purpose uses for the benefit of the remarkable strength and hardness properties imparted to the films crosslinked by TCI.

BRIEF DESCRIPTION OF THE INVENTION It has been surprising to discover that low gloss TCI-crosslinking epoxy films can be obtained using a co-crosslinker dicarboxylic acid in combination with TCI. The effect of the combination of crosslinkers is truly surprising since, as discussed above and as further exemplified herein, the use of each type of crosslinker individually results in a final gloss. According to the present invention, therefore, a novel carboxy-functional crosslinking composition is provided which comprises: (i) 1, 3, 5-tris- (2-carboxyethyl) isocyanurate and / or a salt thereof; and (ii) a dicarboxylic acid crosslinking agent and / or a salt thereof. This novel composition can crosslinker new Carboxy be used in combination with a polyfunctional epoxy compound (polyepoxide) to formulate coating compositions which, when cured under standard conditions, provide crosslinkers, strong, durable and low gloss films. The present invention also includes curable compositions, such as liquid or powder coating compositions, comprising: (a) a carboxy functional crosslinker component comprising (i) 1,3,5-tris- (2-carboxyethyl) isocyanurate and / or a salt of this, and (ii) a dicarboxylic acid crosslinking agent and / or a salt of this; and (b) a main resin component comprising a polyfunctional epoxy compound (polyepoxide). As indicated above, when curing these curable compositions of the invention, films are produced which reduce the relative gloss to films prepared either by 1, 3, 5-tris- (2-carboxyethyl) isocyanurate or the dicarboxylic acid crosslinker alone. The present invention also provides a method of coating a substrate with a low gloss film by applying to a substrate of the curable coating composition as described above then hot-curing the applied coating. In addition, the present invention is a crosslinker film derived from the curable coating compositions of the present invention, and an article coated with such a crosslinker film, these crosslinker films possess excellent firmness, impact and resistance to solvents and also have the desirable characteristic of a uniform low gloss finish. These and other features and advantages of the present invention will be more readily understood by one with ordinary skills in the field when reading the following detailed description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT. 1,3,5-tris- (2-carboxyethyl) isocyanurate (TCI) The TCI is a known compound represented by the formula: The TCI can be prepared from cyanuric acid and acrylonitrile by any of the methods described in US3485833 and US3235553, incorporated even for all purposes as if they were fully exposed, as well as previously incorporated in US5380804. The TCI is a solid at room temperature that has a melting point of 226 ° and 228 ° C.

Dicarboxylic Acid Crosslinking Agents The dicarboxylic acid crosslinking agents suitable for use in the present invention are those suitable for use in coatings and other applications as crosslinkers for epoxy resins. Such dicarboxylic acid cross-linking agents, in general, are well known to persons of ordinary skill in the relevant field, and numerous varieties are generally commercially available.

Such dicarboxylic acids can be represented in general by the formula: HOOC-A-COOH Where A is a hydrocarbylene support. Preferred dicarboxylic acids are monomers in essence, wherein A is a hydrocarbylene group of 1 to 22 carbon atoms. By "hydrocarbylene" is meant a divalent group containing carbon and hydrogen atoms including, for example, alkylene (open chain and branched), aralkylene, alkenylene, and arylene, as well as the corresponding heteroatom containing variations such as the di (alkyl) oxy and the di (aryl) oxy; di (alkyl) carbonyl and di (aryl) carbonyl; hydroxy-substituted alkylene, aralkylene, alkenylene and arylene; and heterocyclics such as furanylene. As specific examples of dicarboxylic acids suitable for use in the present invention can be mentioned 1,3-acetonadicarboxylic acid, adipic acid, azelaic acid, 4,4'-biphenyldicarboxylic acid, 1,1-cyclohexanediacetic acid, 1,4-acid. cyclohexanedicarboxylic acid, 1,4-tetradecanedioic acid, diglycolic acid, 2,2-dimethylglutaric acid, 3, 3-dimethylglutaric acid, dimethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 3,3'-dithiodipropionic acid , 1,2-dodecanedioic acid, ethylmalonic acid, 3-ethyl-3-methylglutaric acid, 2-ethyl-2-methylsuccinic acid, fumaric acid, 3,4-furanedicarboxylic acid, glutaric acid, 1,16-hexadecanedioic acid, acid homophthalmic, maleic acid, malic acid, malonic acid, 3-methyladic acid, 3-methylglutaric acid, methylmalonic acid, methylsuccinic acid, naphthalenedicarboxylic acid, oxalic acid, ortho-, meta-, and para-phthalic acid, pimelic acid ico, sebacic acid, suberic acid, succinic acid, tartaric acid, 1,1-undecanedioic acid and mixtures thereof. Preferred for use in the present invention are 1,2-dodecanedioic acid (DDA) and di-malic acid. Cyclic anhydrides of such dicarboxylic acids (where they exist) are also suitable for use herein, as dicarboxylic oligomers of such dicarboxylic acids with other species of monomers, and dicarboxylic prepolymers of such dicarboxylic acids with diepoxides. For purposes of the present invention, these additional aspects are included within the meaning of dicarboxylic acid crosslinking agent in this broad concept. The particular selection of dicarboxylic acid will, of course, depend on a number of factors recognizable by those of ordinary skill included in the relevant field, but not limited to the desired cure temperature of the final formulated system.

For example, the ordinary skill person in the field can clearly recognize that a dicarboxylic acid which decomposes at a relatively low temperature may not be suitable for high temperature cure applications.

Acid salts. A person of ordinary skills in the field also it recognizes that the organic or inorganic salts of the acids described above can be used in place of the free acids or in combination therewith to effectively produce low gloss coatings of the invention. The organic and inorganic salts of the above dicarboxylic acids can be prepared by mixing the dicarboxylic acid and a suitable base capable of producing the cationic portion of the desired salt. The salt can be isolated or introduced into the coating composition or it can be generated "in situ" by adding the base to the coating composition. As examples of the organic salts may be mentioned the salts of amines such as ammonium, alkylamines, dialkylamines, trialkylamines, aralkylamines, cyclic amines, aromatic amines, arylamines and the like. Preferred without the ammonium, trimethylamine, triethyl amine, tripropylamine, tributylamine, tribencylamine, 1,4-diaza- (2.2.2) -bicyclooctane (DABCO) salts, pyrrolidine, piperidine, morpholine N-methylimidazole, 2-phenyl-2-imidazoline and 4-N, N-dimethylaminopyridine. Suitable examples of inorganic salts include the lithium, sodium and potassium salts.

The carboxy-functional crosslinking composition. As mentioned above, an aspect of the present invention is directed to the carboxy-functional crosslinking composition which can be used in curable compositions for preparing low gloss epoxy coatings. The carboxy-functional crosslinking composition comprises: (i) 1, 3, 5-tris, (2-carboxyethyl) isocyanurate (TCI) and / or a salt thereof; and (ii) a dicarboxylic acid crosslinking agent and / or a salt thereof. As indicated by "and / or", (i) and (ii) are presented as free acids, or as their salts, or as mixtures of free acids and their salts. When powder coating compositions are used, these crosslinker compositions are preferably solid at room temperature, and more preferably are solid at about 40 ° C, to preserve the powder state of the curable composition and prevent lumps from forming. In powder coating applications, non-solid materials or i-solids are also used if, for example, they are absorbed into solid organic and inorganic supports such as, for example, those described in US 5321103 (incorporated by reference even as if they were fully disclosed), which include supports comprising colloidal condensation polymers. The preferred weight proportions of (i): (ii) to obtain a large reduction in brightness are in the range of about 10:90 to about 98: 2, more preferably from about 20:80 to about 98. : 2, they continue more preferably from about 30:70 to about 95: 5, and more especially from about 50:50 to about 90:10.

The main resin component. As indicated above, the main resin component (b) comprises a polyfunctional epoxy compound (polyepoxide), that is, containing an average of at least two and preferably more than two, epoxy groups per molecule. Suitable polyepoxides for use in curable compositions of the present invention may be mentioned those with the following general formula: Where B is an n-functional monomer, an oligomeric or polymeric bridge having n-epoxy groups pendently or terminally attached thereto, and wherein R1, R2 and R3 are the same or different and each is selected from the group consisting of of hydrogen, C 1 -C 4 alkyl, C 1 -C aryl, C 7 -C 11 aralkyl and a mixture thereof (and preferably wherein each is hydrogen), and wherein n is, on average at least two and preferably more than two. The polyfunctional epoxy main resin component in the curable compositions of the present invention contains, on average, at least two and preferably more than two epoxy functionalities per molecule, and includes polyfunctional epoxy groups containing materials which are monomers, oligomers, polymer or a mixture of these. Such polyfunctional epoxy compounds are in general very well known to those of ordinary skill in the field, as exemplified by the following references: US2872427, US3730930, US3752870, US3781380, US3787521, US4011381, US4346144, US4607069, US4650718, US4681811, US4703101, US4764430 , US4855386, US5007173, US5116892, US5118729, WO92 / 19660 and WO94 / 06876, which are incorporated by reference for all purposes as if they were fully disclosed. As specific examples of the monomers of the polyfunctional epoxy compounds may be mentioned difunctional epoxy resins (bisepoxides) which include glycidyl ethers of dihydric phenols similar to the products of the bisphenol-A / epichlorohydrin reaction products such as bisphenol-A diglycidyl; vinyl cyclohexane diepoxides such as diepoxide 4-vinyl-1-cyclohexane; 1,2,5,6-diepoxycyclooctane; 1, 2, 7, 8-diepoxyoctane; diclolopentadiene diepoxide; 1, 4-divinyl benzene diepoxide; Clicklohexane-4-methylcyclohexane-4-carboxylate diepoxide; glycidylated diol, a polyfunctional epoxy group containing materials such as ether diol glycidyl hexane, diglycidyl ethylene glycol ether, diglycidyl ethylene glycol ether, diglycidyl triethylene glycol ether and the like. Other suitable polyfunctional epoxy monomer compounds include trifunctional epoxy resins (trisepoxides) such as tri- (4-glycidyl oxyphenyl) methane and trisiglycidyl isocyanurate; and higher polyfunctional epoxies such as glycidylated pentaerythritol and sorbitol. As an example of commercially available reaction products of bisphenol-A / epichlorohydrin, mention may be made of epoxy resins sold under the Epon® license designation of Shell Chemical Company (Houston, TX) such as Epon® 828 resin having an equivalent weight in the range of 185-192. As an example of a commercially available sorbitol glycylate, the glycidylated sorbitol monomer known as Synocure® 888H resin (Cook Composites and Polymer Company, Port Washington, Wisconsin) can be mentioned. The oligomeric polyfunctional epoxy groups contain materials including oligomeric forms of the monomer materials, diepoxide oligomers such as the low molecular weight bisphenol-A oligomers, prepolymers thereof, reaction products of amines with diepoxides, and the like. The polymeric polyfunctional epoxy group contains materials including, for example, polymers of epoxy groups containing unsaturated monomers and copolymers thereof with unsaturated comonomers which do not contain epoxy groups. As examples of the epoxy groups containing unsaturated monomers, there can be mentioned glycidyl acrylate, glycidyl methacrylate and glycidyl aulic ether. As examples of unsaturated comonomers which do not contain epoxy groups can be mentioned the alkyl esters of acrylic and methacrylic acid containing from 1 to 20 carbon atoms in the alkyl group, such as methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and ethyl hexyl methacrylate; aromatic vinyl compounds such as styrene, methyl styrene vinyl toluene; vinyl and vinylidene halides such as vinyl and vinylidene chlorides, vinyl esters such as vinyl acetate; aulic alcohol; hydroxyalkyl acrylate and methacrylate containing from 1 to 20 carbon atoms in the hydroxyalkyl group such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and the like. The copolymerization reaction of the epoxy group containing unsaturated monomers with pure ethylene-unsaturated epoxy monomers is preferred and can be carried out by known methods such as those described in several of the aforementioned references as well as in US 3787521, US 4181642, EP -A-0480120 and EP-A-0256369, which are also incorporated by reference even as if they were fully disclosed. For example, the preferred epoxy group containing monomers such as glycidyl acrylate, glycidyl methacrylate or mixtures thereof, can be copolymerized with 1 or more pure ethylene-unsaturated epoxy monomers, preferably selected from the group consisting of esters of acrylic acid with alcohols of 1 to 20 carbon atoms, esters of ethacrylic acid with alcohols of 1 to 20 carbon atoms, hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate and methacrylate, acrylic and methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, alpha-methyl styrene , methyl styrene, ethyl styrene, vinyl acetate, vinyl chloride, vinylidene chloride, dialkyl maleates having alkyls of carbon atoms of 1 to 20, dialkylated fumarates having alkyls of carbon atoms of 1 to 20, vinyl toluene, and a mixture of this. The preferred free epoxy monomer is selected from the group consisting essentially of methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, styrene and a mixture thereof. The copolymerization reaction can be carried out by known methods such as those described in the previously incorporated reference US 3787521, US 4181642, EP-A-0480120 and EP-A-0256369. The preferred molecular weight (pro-thio-M weight) of the polyepoxide is in the range of about 1,000 to about 30,000. The epoxy equivalent weight is typically about 50 to about 5000 and the brightness transition temperature (Tg) is between about -20 ° C to about + 120 ° C. Commercially available examples of the glycidyl methacrylate copolymer of the polyfunctional epoxy group contain materials including Synthacryl® resin You see 1436 a product of Hoechst-Celanese Corporation, Charlotte, NC; Estron® GMA-252 resin (Mw: 8300, EW: 250; Tg: 36), a product of Estron Chemicals, Calvert City KY; Ala tex® PD 7110, Almatex® PD 7210 Almatex® PD 7310, Almatex® PD 7610 (M: 7000, EW: 510; Tg: 45) and Almatex® PD 1700, products of Mitsui Toatsu Company, Inc. off Japan, and available from Anderson Develop in Company Adrian, MI; and Blemmer® CP-15 resins (MW: 12300, EW: 1000; Tg: 63), Blemmer® CP-30 (Mw: 10300, EW: 530, Tg: 62) and Blemmer® CP-5SA (Mw: 10100; EW: 3000; Tg: 96), products of Nippon Oil and Fat Corporation off Japan.

Optional ingredients In addition to the main resin components described above, the curable compositions may optionally comprise a variety of additional ingredients normal to any particular end-use choice. A common additional ingredient is a cure catalyst for increasing the cure temperature and / or the cure time of the systems described herein. If present, the cure catalyst is selected from the general groups of basic and nucleophilic compounds, which include phosphines, phosphites, amines, oxides, alkoxides, hydroxides carbonates, carboxylic salts, quaternary salts and the like. Examples of suitable catalysts include alkyl phosphines such as tri-n-octyl phosphine, aryl phosphines such as triphenyl phosphine, alkyl phosphites such as tri-n-octyl phosphite, tertiary amines such as 1,4-diaza- (2.2. 2) -bicylicloctane (DABCO), heterocyclic amines such as imidazole N-methyl and 4-N, N-dimethylaminopyridine, metal oxides, metal hydroxides, metal carbonates, carboxylic acid salts, quaternary salts such as triphenylphosphonium bromide, trimethyl benzyl chloride onium, and trimethylbenzylammonium bromide, metal alkoxides, such as sodium methoxide or tertiary potassium butoxide, and a mixture thereof. Triphenylphosphine and DABCO are the preferred cure catalysts. The present curable compositions may also contain a solvent of the type typically found in coating applications including, for example, alcohols, ketones, esters, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and the like. In floating coating applications, the curable compositions may contain in addition to water, a cosolvent and an aqueous dispersion promoting material such as ethylhexanol, Texanol® (a C8-hydroxyalkyl ester of methyl propionic acid commercially available from Eastman Chemical Company), surfactants and other related materials. Other additional ingredients may be additionally used depending on the particular application. For example, very well known auxiliaries and additives typically used in the coating industry include foam inhibitors, leveling aids, pigments, dispersants, pigment dispersion aids, dryers, UV absorbers. (which include types of hydroxytriasin aryl (such as CYAGARD® Uv 1164 from Cytec Industries Inc.), types of benzotriazole and types of benzophenone), heat stabilizers, other stabilizers such as antioxidants, light stabilizers amine hinders (such as Sandubor® 3058 from Clariant) and the like. Other optional ingredients have been exemplified in many previously incorporated references, and reference can have this for more details. The reference may specifically have US 4344876, US 4619956, US 5106891, US 5322868, US 5461151, EP-A-0434608, EP-A-0444323 and EP-A-0704437, not less of which are incorporated by reference even as if were exposed completely, for detailed discussions of the stabilization of the coatings and other curable compositions with UV absorbers, light stabilizers, amine hinders and / or other types of light stabilizers. Specifically, for powder coating compositions, conventional additives very well known to those of ordinary skill in the art can be employed. Including among these are additives such as fillers, antioxidants, ultraviolet light stabilizers, pigments, for example, pigment Ti02, flow control agents, plasticizers, mold release agents, corrosion inhibitors and the like. Additives such as the bezoin, Modaflow® Powder III Resin Modifier (Monsanto), or Resiflow® P-67 Flow Control Agent (Estron Chemical, Inc.) are preferably incorporated into the powders in about 1 to 4% by weight based level in the total weight of the powder coating.

Reason and proportion of the components. As indicated above it has been surprising to discover that when a combination of 1, 3, 5-tris- (2-carboxyethyl) isocyanurate and a dicarboxylic acid cross-linking agent is used as the cross-linking composition for polyepoxides, a reduction in the brightness of the Cured coatings can be carried out relative to the coating preparations using either the 1,3,5-tris- (2-carboxyethyl) isocyanurate or the dicarboxylic acid cross-linking agent alone. Preferred ratios of 1, 3, 5-tris- (2-carboxyethyl) isocyanurate to dicarboxylic acid crosslinking agent have been discussed above. The weight ratio of the main resin polyepoxide to the carboxy functional crosslinking component in the curable compositions of the present invention is determined primarily by the epoxy weight equivalent of the polyepoxide. Thus, for a given carboxy functional crosslinker, high levels of the crosslinking agent are required. when the polyepoxide used contains a high epoxy content. Usually if a catalyst is employed, high levels of cure catalyst will also be needed in such cases. As a general rule, the resin component and the crosslinker component are mixed in equivalent proportions (equivalents of epoxy to carboxy functionality) from about 0.5: 1 to about 2: 1, and more preferably from about 0.8: 1 to about of 1.2: 1. Typically, this results in a weight ratio of the polyepoxide (b) to the crosslinker component (a) in the range of about 90:10 to about 60:40, but more preferably the ratio is in the range of about 90. : 10 to about 75:25. The amount of the catalyst, if present, is typically in the range of 0.1% by weight to about 5.0% by weight of the total weight of the curable composition.

Preparation and use of curable compositions. The curable compositions of the present invention are suitable for numerous uses including, for example, as adhesives and coatings, in decorative laminated boards, and in the formation of molded crosslinker articles such as engineering composites. The curable compositions can be prepared by mixing several components via methods and in relative amounts which are recognizable by those with ordinary skills in the field in the relevant field depending on the particular end use chosen.

A preferred use especially of curable compositions according to the present invention is in the field of coatings. Any conventional type of coating can be prepared using the curable compositions described herein, including organic solvents based on liquid coatings, floating coatings, powder coatings. In coating applications, the amounts by weight of the crosslinking component and the polyfunctional epoxy compound depends on the factors including, for example, the particular materials chosen, the presence of other reactive species as well as the desired end use. Based on these variables and others, those with ordinary skills in the field may be able to adjust the composition of the coatings (which include the relative amounts of the components) to carry out the desired effect. Organic solvents based on liquid coatings in accordance with the present invention can be prepared via conventional means by adding within the commonly used organic coating solvents the components of the curable composition and the optional ingredients, if present, in any convenient order. In organic solvents based on coatings, the systems are formulated to produce solids containing levels suitable for their convenient application with the minimum of lost material, preferably at a level of solids contents in the range of about 20% by weight to about 85% by weight, and more preferably at a level of solids content in the range of about 45% by weight to about 80% by weight, depending on the application method chosen. The floating coating compositions according to the present invention can be prepared by combining the components of the coating in any particular order, but it is preferred to make by preparing a dispersible composition by substantially and homogeneously mixing the coating components with an active surface material (which can be being an inherent property of the resin component), to then disperse the dispersible composition in an aqueous medium, which may comprise only water or may contain other components in minor amounts of water-miscible cosolvents for easy dispersion or adjusting the viscosity. The floating coating compositions can be formulated at various solid contents, generally in the range of about 20% to about 75% by weight solids, but preferably in the range of about 20% to about 50% by weight of solids. solids, depending on the chosen application method. The powder coating compositions according to the present invention can be prepared by any known method, for example, by dry mixing the components in a mixture followed by the combination in an extruder and granulation, grinding and then selecting it for obtain a coating powder of a suitable mesh size. For powder coating applications, compositions containing in crosslinking solids and major resin components are preferred. Alternatively, some or all of the components can be dissolved in a solvent such as methylene chloride and dry sprayed by well-known techniques. The coating compositions of this invention can be formulated for use in numerous areas such as original manufacturing equipment (OEM) including automotive coatings, general industrial coatings including coatings for industrial maintenance, architectural siding, can lining and Similar. They are used as cable coatings, applications, automotive parts, furniture, tubing, machinery, and the like. The suitable surface includes metals such as steel and aluminum, plastics, wood and glass. Coating method. The present coating compositions are used for applying the coating to a substrate and then curing the application of the coating to form crosslinking films. Liquid coatings can be applied, for example, by immersing them, by spraying them, by filling them, by brushing them, by flow, by electro-coating or by electrostatic spraying. After application, the liquid carrier (e.g., organic solvent and / or water) is generally allowed to evaporate partially to produce a uniform coating on the substrate. The powder coatings can be applied, for example, by means such as gun powder, electrostatic deposition or deposition of a fluidized bed. After deposition, the powder is typically heated to a temperature sufficient to cause the particles to soften, melt, and flow begin to heal. Completely curing the present coating composition (and curable compositions) generally requires temperatures in the range of about 25 ° C to about 400 ° C depending on the components as well as the final application use. In liquid coating applications, the cure temperature is typically in the range of about 80 ° C to about 60 ° C. In powder coating applications, the cure temperature is typically in the range of about 100 ° C to about 250 ° C, preferably about 110 ° C to about 230 ° C, and more preferably in the vicinity of about 100 ° C. 150 ° C to about 230 ° C, and much more preferably between about 170 ° C to about 200 ° C. In roll coating applications, the cure temperature is typically in the range of about 250 ° C to about 450 ° C. The type of cure is preferably in the range of about 1 second to about 30 minutes but may vary depending on the temperature chosen for the cure. For example, a fully cured roll coating can be obtained either by curing at 260 ° C for one minute or curing at 417 ° C for 20 seconds. Typical cure times for liquid and powder coatings are in the range of about 5 minutes to about 30 minutes. The superior unexpected properties of the coating compositions of the present invention include the ability to produce films which have low gloss, good firmness, and high impact and solvent resistance.The coating compositions of the present invention are generally capable of producing substantially durable surfaces, free defect films of suitable thickness or thickness and are particularly suitable for applications requiring films of thickness in the range of about 1 mil to about 2.5. Thousands. Such applications include a wide variety of general industrial uses including, for example, uses such as cartridges, cartridge surfaces, instrument linings, interior and exterior furniture coverings, garden and meadow equipment, and air conditioning units for the household, and automotive coatings that include, in particular, ornaments vehicle parts, black exteriors, windshield wipers, and under bonnet areas. The following examples are offered to illustrate various aspects of the invention and may not be constructed as a limitation of the invention's field.

EXAMPLE 1 A. Preparation of 1, 3, 5-tris- (2-cyanoethyl) isocyanurate. To a 100 ml round bottom flask is added 64.5 g of cyanuric acid alone with 300 ml of water, a stir bar is added, and then 50 g of triethylamine was charged. The solution is stirred for 30 minutes at room temperature. Then 87 grams of acrylonitrile is added to the solution. The solution is heated under reflux for 12 hours. The solution is then cooled to room temperature and the solid precipitate is filtered. The dry solid weighed 133 g (92%). The range of the melting point is between 222 ° C-224 ° C.

B. Preparation of 1, 3, 5-tris- (2-carboxyethyl) isocyanurate. A 500 ml round bottom flask is added 94 g of tris- (2-cyanoethyl) isocyanurate alone with 200 ml of a 36% solution of hydrochloric acid. The solution is heated under reflux for 4 hours, filtered through a glass funnel, and left at room temperature.

The obtained crystals weigh 105 g (98%). The range of the melting point is between 226 ° C-228 ° C.

EXAMPLE 2 Using the following general procedure, eighteen powder coated panels were prepared as follows: 1,2-dodecanedioic acid (DDA) or dl-malic acid, 1, 3, 5-tris- (2-caroxyethyl) isocyanate (TCI) ), Almatex® PD-7610 (PD-7610), and the optional ingredients listed in tables 1-9 are mixed and fused in a roller mill at approximately 125 ° C for about 5 minutes, the resulting mixture is crushed and classified in a powder layer with a particle size of 35 microns (plus or minus 10 microns). The resulting powder coating composition is applied to 1000 Bonderite® planks (Parker Chemical Company) by electrostatic spraying. The coated panels are placed horizontally in a mechanically forced convection convection oven at the temperature / time specific cure cycle and curing. Preparatory details and physical and strength properties of the cured coatings are summarized in Tables 1 to 9.

Table 1 B TCI / DDA 0/100 0/100 DDA 13.80 13.80 PD-7610 66.20 66.20 R960-48 20.00 20.00 RESIFLOW P-67 1.00 1.00 substrate BO 1000 BO 1000 Temp of the oven (° C) 175 190 Baking time 20 20 Scraper Mek 200+ 200+ Appearance of smooth smooth film Thickness of the film 1.5 / 2.4 0.7 / 1.4 KHN 13.9 13.9 Firmness of the HB-F HB-F pencil Impact F / R (in.lbs) 20/5 50/5 brightness 60 degrees 89.6 88.1 degrees 75.0 69.6 Table 2 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8 Table 9 While the present invention has been described with reference. to certain preferred embodiments, those modifications and variations are apparent these may be made by those skilled in the art other than deviating from the scope of the invention as defined by the appended claims.

Claims (13)

1. A carboxy-functional crosslinking composition characterized in that it comprises: (i) 1, 3, 5-tris- (2-carboxyethyl) isocyanurate and / or a salt thereof, and (ii) a dicarboxylic acid crosslinking agent and / or a salt thereof. , where the weight ratio of (i): (ii) is from about 20:80 to about 98: 2.

2. The carboxy-functional crosslinking composition according to claim 1, characterized in that in the dicarboxylic acid cross-linking agent represented by the formula: HOOC-A-COOH wherein A is a hydrocarbylene group of 1 to 22 carbon atoms.

3. The carboxy-functional crosslinking composition according to claim 1, characterized in that the dicarboxylic acid is 1,2-dodecanedioic acid.

4. The carboxy-functional crosslinking composition according to claim 1, characterized in that the ingredients (i) and (i) are solid at room temperature.

5. A curable composition, comprising (a) a carboxy-functional crosslinking component and (b) a resin component comprising a polyfunctional epoxy compound, characterized in that (a) is a carboxy-functional crosslinking composition as set forth in any of claims 1 -4.

6. The curable composition according to claim 5, characterized in that the polyfunctional epoxy compound is a copolymer derived from the copolymerization of an epoxy group containing an olefinically unsaturated monomer and a free olefinically unsaturated epoxy monomer.

7. The curable composition according to claim 6, characterized in that the copolymer has a molecular weight (Mw) in the range of about 1. 000 to about 30,000; an epoxy of equivalent weight of about 50 to about 5,000; and a barometric transition temperature of about -20 ° C to about 120 ° C.

8. The curable composition according to claim 5, characterized in that it further comprises a catalyst cure in an amount in the range of about 0.01 weight percent to about 5.0 weight percent of the total weight of the curable composition.

9. The curable composition according to claim 5, characterized in that the weight percent of the resin component (b) to the carboxy-functional crosslinking component (b) is in the range of about 0.5: 1 to about 2: 1. .

10. A powder coating composition comprising a carboxy-functional crosslinking component (b) a resin component comprising a polyfunctional epoxy component, the components (a) and (b) is solid at room temperature, characterized in that it is the carboxy crosslinking composition. -functional as set forth in any of claims 1-4.

11. A method of coating a substrate with a low gloss coating, characterized in that said method comprises the steps of: (A) applying the substrate to a curable coating composition, comprising (1) a carboxy-functional crosslinking component and (2) ) a resin comprising a polyfunctional epoxy component; and (B) which thus cures the application of the curable composition to form a crosslinking film, characterized in that (A) (1) is the carboxy-functional crosslinking composition as set forth in any of claims 1-4.

12. The method according to claim 11, characterized in that the coating composition is a powder coating composition.

13. A substrate coated with a low gloss crosslinking film characterized in that it is derived from the curable composition of claim 5.