MXPA00012864A - Aminoplast anchored trisaryl-triazine uv absorber - Google Patents

Abstract

A novel class of UV absorbers, ortho-hydroxyphenyl substituted triazine compounds bonded to aminoplast resins is provided. Compared to unanchored stabilizers, the anchored stabilizers disclosed herein have increased compatibility with coating resins and have reduced volatility due to higher molecular weights resulting from anchoring. A process for preparing the anchored stabilizers by the reaction of triazines containing active hydrogen with alkoxymethylated aminoplasts in the presence of a catalytic amount of acid. The novel ortho-hydroxylphenyl substituted triazine compounds are bound to the aminoplast resins by carbon-oxygen, carbon-carbamoyl nitrogen or carbon-active methylene carbon linkages. The aminoplasts include alkoxymethylated derivates of glycolurils, melamines, and urea-formaldehyde resins.

Description

UV ABSORBENT, BASED ON TRIS-ARIL-TRIAZINA ANCHORED IN AMINOPLASTIC FIELD OF THE INVENTION This invention relates to the preparation and use of novel ultraviolet light stabilizers based on triazine anchored in aminoplast. BACKGROUND OF THE INVENTION The stabilization of polymers by incorporating ultraviolet light stabilizers, particularly UV light absorbers of trisaryl triazines into polymer films, coatings, fibers and molded articles to provide protection against the light, moisture or oxygen degrading action, has been an active area of work in recent years. However, deficiencies such as solubility in solvent coatings and formulations, volatility and generally poor solubility and poor retention of existing stabilizers within a polymer matrix, still remain substantially unresolved. For example, attempts to reduce volatility by using oligomers and polymers of higher molecular weight have generally resulted in decreased retention of the stabilizer due to incompatibility. The capacity of extraction and migration of the stabilizer on the surface eventually lost as a result of incompatibility or low molecular weight, are still serious problems plaguing the plastics industry. Limited attempts to increase the molecular weight of the tris-aryl triazine stabilizer without introducing incompatibility when using anchor groups have been carried out in the past with great success. More recently, U.S. Patent Nos. Nos. 5,547,753; 5,612,084 and 5,621,052 have described UV absorbers anchored in aminoplast, which have a carbon-carbon bond. The processes to produce these compounds, however, require concentrated sulfuric acid as a solvent. The use of sulfuric acid as a solvent has several disadvantages, including the difficulty of handling on an industrial scale, isolation of the sulfuric acid product and oligomerization of amino resins in insoluble materials. Furthermore, the use of sulfuric acid is not practical for triazines that contain functionalities that are unstable in strong acids. Thus, there remains a need for a process for producing the products anchored in aminoplastics having higher molecular weight, low volatility, improved solubility and compatibility with the polymer matrix. Accordingly, an object of the invention is to provide a novel class of triazine compounds bound to aminoplast resins such as alkoxymethylated melamines by active carbon-methylene carbon bonds and carbamoyl carbon-carbon and oxygen-oxygen bonds. Another object of this invention is to provide a process for the preparation of the novel stabilizers of the invention. A further object of the invention is to provide a process for producing the compounds having higher molecular weight, low volatility and improved solubility and compatibility with the polymer matrix. Yet another objective of this invention is to provide curable compositions containing the novel stabilizers of the invention and also provide stabilized cured compositions that are obtained by curing the curable compositions. Yet another object of this invention is to provide an improved method for stabilizing polymers, wherein the improvement comprises adding to the polymers, the novel stabilizers of the present invention. SUMMARY OF THE INVENTION The present invention provides a novel class of UV absorbers, triazine compounds substituted with ortho-hydroxyphenyl linked to aminoplast resins, such as alkoxymethylated melamines, glycolurils and urea formaldehyde resins. This invention is also a process for preparing the novel UV absorbers of the invention. This invention is also a curable composition containing the novel UV absorbers of the invention. This invention also relates to an improved method for stabilizing polymers wherein the improvement comprises adding to the polymers the novel stabilizers of the invention. The advantages of the anchored stabilizers of this invention against their non-anchored precursors include in general, superior solubility and compatibility with polymers and resins, reduced migration between layers of coating film and in general lower volatility due to higher molecular weights. DETAILED DESCRIPTION OF THE INVENTION The novel composition of this invention is a new class of UV absorbers illustrated below, triazine compounds substituted with ortho-hydroxyphenyl linked to aminoplast resins such as alkoxymethylated melamines, glycolurils and urea formaldehyde resins.

CH (R1 °) lf * (CH (R10) OR9) m-n link: A is a m-functional monomeric or oligomeric aminoplast anchor molecule having at least 0.1 mole of trisaryl-1,3,3-triazine UV absorber bondable per aminoplast anchor molecule bonded through n bridging groups, these bridging groups are selected from methylene groups and -CHR10 - R <R8> each independently is selected from hydrogen cyano, chloro, bromo, nitro, alkyl having 1 to 24 carbon atoms, aryl with 6 to 24 carbon atoms, aralkyl with 7 a 24 carbon atoms, hydroxy, alkoxy with 1 to 24 carbon atoms and alkyl with 1 to 24 carbon atoms optionally substituted by one or more oxygen atoms and / or carbonyl groups, with the proviso that at least one of R ^ R8 is ortho to the triazine ring connection point and is a latent hydroxyl or hydroxyl group blocked with an alkyl, phenyl, aryl, acyl, aryl acyl, aminocarbonyl, phosphonyl, sulfonyl or silyl group containing 1 to 18 carbon atoms; X and X1 are independently a direct bond, a straight or branched chain alkylene group with 1 to 24 carbon atoms, a straight or branched chain alkylene group with 1 to 24 carbon atoms terminated or interrupted by one or more groups selected from -O-, -NH-, -NR9-, -CONH-, -CONR9 , one or more carbonyl groups or combinations thereof; I I Y is a direct bond CONR9-, -Z-CR9-Z 'or -Z-N-Z', wherein Z is -CO-, -CO ~ M +, -CONR9, -SO- or -S02; and Z 'is -COOR9, -COOM +, -CHO, -COR9, -CONR9, -CN, -N02, -SOR9, -S02R9, -S02OR9, -S02NR29; R9 and R10 independently are selected from the group consisting of hydrogen, linear or branched alkyl with 1 to 24 carbon atoms, aryl with 6 to 24 carbon atoms or aralkyl with 7 to 24 carbon atoms; m is at least 1; and n is at least 0.1.

The broad discovery of this invention is that by chemically combining anchors of amino resins and certain bondable trisaryl 1, 3, 5-triazine UV absorbers, they produce compositions of matter that surprisingly retain the stabilizing effect of the tris-aryl triazine UV absorber. , allows combinations of different bonding UV absorbers in the same composition and achieves advantageous properties of the amino resins such as improved solubility and compatibility with coating solvents and reduced volatility. For example, the gain in solubility that is achieved by reacting trizaril-s-triazine UV absorbers bindable with amino resins, not only makes those compositions more soluble and compatible with the solvents and coating formulations, but also makes the compositions more compatible with the final cured coating film, thereby minimizing surface efflorescence, extraction capacity and the resulting loss of the stabilizer to the environment. Also, the molecular weight gain that is achieved by reacting trizaril-s-triazine UV absorbers bindable with amino resins makes the composition less volatile, thereby minimizing losses due to high temperature baking.

The present invention provides a wide variety of anchored stabilizers due to the ability to change any of the following variables: 1.- The type of amino resin anchors. 2. - The type of one or more substituted triazine triazine reagents. 3. - The degree of reaction of (1) and (2) (substitution ratio). The following sections of this detailed description will illustrate useful types of amino resins to form the novel compounds of the invention. By way of example, the specific use of the following types of amino resins is set forth below: 1. Melamine-type resins 2. Glycoluril-type resins 3. Urea-formaldehyde resins The following sections will also illustrate the variety of novel compounds that result from the degree of reaction between the amino resin anchor and the stabilizer. The amino resin anchor can be completely or partially reacted with the stabilizer, creating three categories of novel compounds as follows: 1. Stabilizing compounds / amino resin wherein the stabilizer is substantially averaged with all reactive sites available in the amino resin . This results in a novel compound having a high degree of stabilizing activity and reduced volatility. 2. - Stabilizing compounds / amino resin wherein the stabilizer on average is reacted with all but one of the reactive sites available in the amino resin. This results in a novel compound that can chemically combine with plastics known to react with amino resins to give a secondary group with stabilizing functionality. 3. - Stabilizing compounds / amino resin wherein the stabilizer on average is reacted to leave two or more reactive sites available in the amino resin. This results in a novel compound that can act chemically as an entanglement agent. These novel entanglement agents also act as stabilizers. The word "stabilizer" as used herein means the ortho-hydroxyphenyl substituted triazine compounds of the present invention. These compounds are known to be useful for preventing degradation by environmental forces, including ultraviolet light, actinic radiation, oxidation, humidity, atmospheric pollutants and their combinations. The novel substituted trisaryl triazines anchored with aminoplast, optionally in combination with other UV stabilizers of the invention have monomeric or oligomeric aminoplast cores having more than 0.1 mole triazine triazine triazine UV stabilizing groups substituted per mole of aminoplast connected secondarily with methylene bridges. Generically, the novel stabilizers of this invention can be represented by the following formula: (UV Absorbent) n-A- (CH (Rl10) OR 9) mn wherein at least one UV absorber is a tris aryl-s-triazine bondable as describes in the present invention; A is a monomeric or oligomeric aminoplast anchor molecule that serves as a core to support the tris-aryl substituted triazine UV stabilizing groups secondarily connected; and n is a number having a minimum average value greater than 0.1 and a maximum value equal to the number of reactive stabilizing groups present in the aminoplast anchor.

The stabilizing reactive group in the aminoplast anchor molecule is typically an alkoxy methyl group but other reactive groups such as hydroxy, acyloxy, halo, mercapto, sulfonyl, sulfonate, sulfate, phosphate, dialkylsulfonium, trialkylammonium, and the like can be employed. Specifically, it should be noted that in addition to the linkable trisaryl-1, 3, 5-triazine groups described above, bondable UV absorbers of other classes can also be combined in the same aminoplast anchor molecule. Thus, in addition to the linkable trisaryl-1, 3, 5-triazine groups of the present invention, any one or more of the following classes of UV absorbent may be present: (1) other 2- (2-hydroxyphenyl) -1, 3, 5-linkable triazines (2) 2- (2-hydroxyphenyl) benzotriazoles bondable (3) bondable 2-hydroxybenzophenones (4) bondable 2-hydroxyoxanilides (5) linkable salicylic acid derivatives (6) latent derivatives of (1) to (5), wherein the phenolic 2-hydroxyl group is blocked with a blocking group convenient The presence of more than one kind of UV absorber in the same amino resin molecule, for example the combination of a linkable 2- (2-hydroxyphenyl) -1,3,5-triazine and a - (2-hydroxyphenyl) benzotriazole bindable in the same molecule, provides a novel composition with UV absorbance over a broad spectral range. More preferred embodiments of the invention are UV absorbers of the above formula wherein A is a melamine anchor. wherein: A is an energetic monomeric or oligomeric aminoplast anchor molecule to which n bondable trisaryl-1, 3, 5-triazine UV absorbers are attached through a methylene bond; X, X 'and Y are as described above; R1, R2, R6 and R7 independently are chosen from hydrogen, chlorine, cyano, alkyl with 1 to 24 carbon atoms, aryl with 6 to 24 carbon atoms and aralkyl with 7 to 24 carbon atoms; and R9 is alkyl with 1 to 5 carbon atoms. AMINOPLASTIC ANCHORES The aminoplast anchor molecules of this invention are aminoplast interlayers commonly used in coatings, molded parts and adhesives. The term "aminoplast" is defined herein as a class of resins that can be prepared by the reaction of a compound containing amino group and an aldehyde. The reaction product of compounds containing amino and aldehyde group is often reacted more with an alcohol to produce partially or completely alkylated derivatives. These derivatives are included in the definition of "aminoplast" given above. The term "aminoplast" as used in the context of this invention typically comprises a polyfunctional amino resin which may be monomeric or oligomeric. For example, in the preparation of aminoplastics from compounds containing amino group and aldehydes and subsequent alkylation, dimeric and oligomeric products resulting from autocondensation reaction are often obtained. These oligomeric autocondensation products are included in the definition of "aminoplast" given above. By way of example, the aminoplast anchors A of this invention include the groups represented by the following formulas: O O (CH (R10) OR9) m-n N C N polyfunctional carbamates; polyfunctional amides; hydantoins; dialcoxyethylene ureas; dihydroxyethylene urea represented by the formula: homopolymers and copolymers containing carbamate units of the formula: its oligomeric derivatives; and monomeric and oligomeric partially methylolated or substantially fully methylolated, non-etherified or partially etherified aminoplastics; wherein R1 is hydrogen or a linear or branched alkyl group with 1 to 24 carbon atoms.

R11 and R12 independently are hydrogen alkyl or alkyl or aryl groups with 1 to 24 carbon atoms; R 13 is an aliphatic or cycloaliphatic alkyl group with 1 to 24 carbon atoms; an aromatic group with 1 to 24 carbon atoms; or an aralkyl group with 1 to 24 carbon atoms; and R14 is hydrogen or alkyl having 1 to 24 carbon atoms and a is at least 1; and its oligomeric derivatives. The aminoplast can have as substituents a hydrogen, an alkyl or aryl group with 1 to about 20 carbon atoms or a stabilizing reactive group such as -CH 2 OH and -CH 20 R 9 wherein R 9 is an alkyl group 1 to about 20 carbon atoms or a oligomeric group containing aminoplast group, provided that the total number of reactive stabilizing groups per each aminoplast anchor is at least one and preferably more than one. Preferred aminoplast anchors of this invention are substantially monomeric aminoplast interlayers, substantially completely methylolated, substantially completely etherified, which are commonly employed in the coating industry. They are characterized in that they have at least two and preferably more than two stabilizing reactive groups per anchor molecule. The most preferred aminoplast anchors of the invention are chosen from a group consisting of glycoluril, melamine, benzoguanamine, cyclohexanecarboguanamine, urea and their mixtures substantially fully etherified, substantially methylolated in complete form, substantially monomeric. In addition to the substantially monomeric amine-aldehyde aminoplast anchors, substantially completely etherified, monomeric and oligomeric aminoplasts totally methylolated in substantially or partially methylolated, non-etherified or partially esterified form are also usable in the compositions of this invention. Aminoplast anchors containing very few alkoxy methyl groups generally have low solubilities due to high N-H levels and thus are less preferred. The most preferred aminoplast anchors are exemplified in greater detail below. MELAMINE ANCHORS The melamine-based aminoplast anchors of this invention are well known per se and have been used extensively as effective interlayers in coatings. The melamine anchors of this invention are represented by the formula: wherein: R9 is hydrogen or a linear or branched alkyl group with 1 to 24 carbon atoms. Unlike the extra-functional glycolurils, the alkoxy methyl melamine functionality can be a maximum of 6 in an effective stabilizing range with 1 to 6 reactive stabilizing alkoxy methyl groups per melamine molecule. Like the glycolurils in addition to monomers, the alkoxy methyl melamines can contain dimers, trimers, tetramers and higher oligomers, each combination of monomers and oligomers is preferred for a given application. For example, compositions rich in lower viscosity monomers are preferred for solvent-based high solids coatings. An example of substantially monomeric melamine, methylolated in substantially complete form, and etherified in substantially complete form used in this invention consists of CYMELM 303 Melamine Interlacing Agent, a product of Cytec Industries., Inc., West, Paterson, NJ, which has the following formula and properties: Non-volatile (% by weight) *: 98 color, maximum (Gardner 1963): Viscosity 1 (Gardner-Holt, 25 ° C): free formaldehyde of X-Z2, maximum (% by weight): 0.5 degree of polymerization: 1.75 * Sheet method (45 ° C / 45 min). Another example of a substantially monomeric melamine, substantially methylolated in complete form, and substantially fully etherified, is the aminoplast resin CYMELMR 1168 a product of Cytec Industries, Inc., West, Paterson, N.J. The alkyl group in CYMELMR 1168 consists ntially of a mixture of the methyl and isobutyl groups. It has the following formula (where R = methyl or isobutyl) and properties: Non-volatile (% by weight) *: 98 Color, maximum (Gardner 1963): 1 Free formaldehyde, maximum (% by weight): 0.5 Viscosity (Gardner-Holt, 25 ° C): X-Z2, Equivalent weight: 150- 230 * Blade Method (45 ° C / 45 min.) An example of a substantially oligomeric, partially etherified, methylolated melamine is substantially the crosslinking agent CYMELMR 370, a product of Cytec Industries, Inc., West Paterson, NJ It has the following properties: Non-volatile (% by weight) *: 88 + 2 Solvent: Isobutanol Viscosity (Gardner-Holt, 25 ° C): Z2-Z4 Color, maximum (Gardner 1963): 1 Equivalent in weight: 225-325 * Foil Method (45 ° C / 45 min.) Glycoluril anchors The glycoluril anchors of this invention are N-substituted glycolurils represented by the formula: wherein at least two of the R groups are selected from the group consisting of methoxymethyl, ethoxymethyl , propoxymethyl, butoxymethyl, pentoxymethyl, bexoxymethyl, heptoxymethyl, octoxymethyl, nonoxymethyl, decoymethyl and their mixtures and the remaining R groups are chosen from hydrogen, alkyl hydroxymethyl and glycoluril group containing oligomeric portions. While it is preferable to have a multiplicity of alkoxy methyl groups per each glycoluril anchor molecule under ordinary circumstances, it is not necessary to have, for example, a tetra-substituted monomeric aminoplast, such as X, N ', N' 'N' '- tetraalkoxymethylglycoluril represented by the formula: wherein R is an alkyl group with 1 to about 20 carbon atoms. Glycoluril can contain monomeric as well as oligomeric components. Monomeric tetraalkoxiglycolurils themselves are not considered resinous materials since they are as individual entities, non-polymeric compounds. It is considered, however, that they are potential resin-forming compounds when subjected to heat and particularly when subjected to heat under acidic conditions. As a result of the resin-forming ability described, the substantially monomeric glycoluril aminoplast of this invention can produce, during the course of the reaction, varying amounts of oligomeric components such as dimers, trimers and tetramers. The presence of varying amounts of these oligomeric forms is permissible and undoubtedly beneficial particularly in cases where products of higher molecular weights and lower volatility are desired as in the case of most applications where the products are used as stabilizers against the Degrading action of UV light. An example of glycoluril anchors of this invention is powdered aminoplast resin POWDERLINKMR 1174 a product of Cytec Industries, Inc., West Paterson, N.J. It has the following formula and properties: Non-volatile, minimum (% by weight): Appearance 98: Granulated flakes pale yellow white melting point (° C): 90 ° -110 ° C. Average molecular weight: 350 equivalent weight 90-125 Another example of a usable glycoluril anchor in this invention is fully butylated glycoluril resin CYMELMR 1170 a product of Cytec Industries, Inc., West Paterson, NJ which has the following properties: Non-volatile, minimum (% by weight): appearance 95: light liquid color, maximum (Gardner 1963): Viscosity 3 (Gardner-Holt, 25 ° C.): average molecular weight X-Z2: 550 Equivalent Weight: 150-230 Methylol Content: Very Low UREA ANCLAS An example of a urea used in this invention is BEETLEMR 80 butylidene formaldehyde resin a product of Cytec Industries, Inc., West Paterson, NJ, which has the following properties : Appearance: Light Liquid Color, Maximum (Gardner 1963): 1 Non-Volatile (% by weight) * 96 + 2 Viscosity (Gardner-Holt, 25 ° C) Solvent Tolerance X-Z3 (ASTM D1198-55): * Sheet method > 500 (45 C / 45 min.) GUANAMINE ANCLAS As in melamines, alkyl or aryl guanamine aminoplasts partially or fully methylolated or etherified, both in their monomeric and oligomeric forms, are used as anchors in this invention, with the selection depending on of the particular application or the properties that are desired in the product. The aminoplasts of benzoguanamine, cyclohexyl carboguanamine and acetoxyguanamine, are especially preferred as anchors in this invention. Benzoguanamines are represented by the formula: wherein R is an alkyl group with 1 of about 20 carbon atoms, or a mixture thereof. An example of an anchor based on benzoguanamine is the CYMELMR 1123 resin as described above, wherein R is a mixture of methyl and ethyl groups. Anchors based on guanamine aceto are represented by the formula: wherein R9 is an alkyl group of 1 to about 20 carbon atoms, or a mixture thereof.

The anchors based on cyclohexylcarboguanamines are represented by the formula: wherein R is an alkyl group with 1 of about 20 carbon atoms, or a mixture thereof. It is evident from the foregoing that a person skilled in the art, to select suitable anchors for a particular application, may choose a mixture thereof which imparts a balance of properties desired for this particular application. AMINOPLASTIC ANCHORED STABILIZERS The alanoplast-anchored tri-aryl 1,3-triazine UV stabilizers of the present invention are represented by the formula: O-X'-Y "CH (R10) - (CH (R10) OR9) m-n wherein A is a functional an aminoplast anchor molecule to which trisaryl-1,3,5-triazine n-molecules bondable through n methylene (or alkylidene) bridges are connected, the aminoplast anchor molecules are selected from the group consisting of : O o (CH (R10) OR9) m-n II N c C N 15 25 polyfunctional carbamates; polyfunctional amides; hydantoins; dialcoxyethylene ureas; dihydroxyethylene urea represented by the formula: homopolymers and copolymers containing carbamate units of the formula: its oligomeric derivatives; and monomeric and oligomeric aminoplasts substantially methylolated in fully or partially methylolated, non-etherified or partially etherified forms; wherein R9 is hydrogen or a linear or branched alkyl group with 1 to 24 carbon atoms. R11 and R12 independently are hydrogen alkyl alkyl or aryl groups with 1 to 24 carbon atoms; R 13 is an aliphatic or cycloaliphatic alkyl group with 1 to 24 carbon atoms; an aromatic group with 1 to 24 carbon atoms; or an aralkyl group with 1 to 24 carbon atoms; and R14 is hydrogen or alkyl having 1 to 24 carbon atoms and is at least 1; Preferred novel aminoplast-anchored trisaryl-substituted 1, 3, 5-triazine UV-absorbents of the present invention are those wherein A is a melamine anchor, m is about 1 to 5 per melamine ring, n is between about 1 to 5. per melamine ring, the ratio of trisaryl 1,3,5-triazine bondable to melamine anchor is from about 1: 1 to 5: 1 and wherein the melamine anchor is a mixture of monomeric, dimeric, trimeric, tetrameric and higher oligomeric units which are bridged by methylene or methylene-oxy-methylene groups. More specifically, the preferred novel aminoplast anchored trisaryl 1,3,3-triazine UV absorbers of the present invention have the following general formula: The above formula is an idealized structure representing 1: 1 adducts of hexalkoxylmethyl melamine with UV absorbents trisaryl-1,3,5-triazine bondable. The formula is used for reasons of clarity. Each of R1 -R9, X, X 'and Y are as described above. The amino resin adducts of the present invention are derived from the reaction of trisaryl triazine UV absorbers substituted with an active hydrogen, these UV absorbers are described by the following general formula: wherein: the group -XO-X'-YH can be selected from -0 (CH2) NOH N = l-24 -OCH2CH (OH) CH3 -OCH2CH (OH) (CH2) 3CH3 -OCH2CH (OH) (CH2) 5CH3 -OCH2CH (OH) (CH2) 7CH3 -OCH2CH (OH) (CH2) nCH3 -OCH2CH (OH) Ph -OCH2CH (OH) (CH2) 9CH3 -OCH2CH (OH) CH2OH -OCH2CH (OH) CH2OC4Hg -OCH2CH (OH) CH2OC6H13 -OCH2CH (OH) CH2OC8H17 -OCH2CH (OH) CH2OCH (C2H5) C5H10 -OCH2CH (OH) CH20 (C13H27 to C15H31) -OCH2CH (OH) CH20 (C12H25 to C14H29) -OCH2CH (OH) CH2OPh -OCH2CH (OH) CH2OCOC9H19 -OCH2CH (OH) CH2OCOC10H21 (Mixture of isomers) -OCH2CH (OH) (CH2) OCOC (CH3) = CH2 -OCH2CONEt (CH2) 2OH -OCH2COO (CH2CH20) 3H -OCH2COO (CH2CH20) 7H -OCH2COOCH2CH (OH) CH2OCOCH = CH2 -0 (CH2CH20) nH n = 7- 9 OH I CH3 (CH2) 7CH-CH- (CH2) 7COOC8H17 O -OCH2CH (OH) CH2OCH 2 -OCH2CH (OH) CH2OCOCH = CH2 -OCH2CH (OH) CH2OCOC (CH3) = CH2 (CH2) n CH, (CH2) n- (CH2) - CH2 CH2"(CH2) n CH, I OH where n = l-24, n ^ O-23, n2 = l-50, n3 = l-24 Additional triazines containing active hydrogen are carbamoylate derivatives of any of the above hydroxy functional triazines, this is triazines containing the functionality -CO (0) NHR9 Additional triazine precursors containing an active methylene are also convenient. In this case -YH is -Z-CHR-Z 'or Z-NH-Z' wherein: Z is -CO-, -CO ~ M +, -CONR9, -SO- or -S02; and Z 'is -COOR9, -COO "M +, -CHO, -COR9, -CONR9, -CN, -N02, -SOR9-, -S02R9 -S02OR9, or -S02NR29; and wherein the Z group is linked to any of the hydroxy functional triazines listed above. PROCESS FOR PREPARATION The monomeric or oligomeric triazine UV absorbers anchored in aminoplast of the present invention are prepared by reacting a functional triazine UV absorber with an amino resin, for example a melamine guanimine resin (benzoguanimine, cyclohexylguanamine and acetoguanimine), glycouril or urea-formaldehyde. Suitable reactive functionality for the triazine UV absorbent are active hydroxyl, carbamoyl and methylene (eg, acetoacetate or malonate). Functional hydroxyl UV absorbers are well known in the art. The driving force for the acid-catalyzed reaction between the reactants is the generation, from a methylated alkoxy or methylated hydroxy aminoplast reagent, of an electrophilic center positively charged to the methylene group of the methyl or hydroxy methyl alkoxy connected to the aminoplast by elimination of the elements of an alcohol or water of the protonated aminoplast. The positively charged electrophilic center then reacts with the electron-rich triazine hydrocarbon group enol (electron-activated methylene derivative). The ratio of functional triazine to amino resin depends on the number of active methylol or alkoxy methyl groups present in the amino resin. The equivalents of the functional triazine are equal to or less than the equivalents of the methylol or alkoxy methyl groups. For example, CYMEL MR 300 has almost six equivalents of alkoxy methyl groups. Therefore, the ratio of functional triazine to amino resin is from 0.1 to 6. The preferred molar ratio is from 1 to 3. The reaction is carried out in an inert solvent, preferably an aromatic solvent such as toluene or chlorobenzene, in the presence of an acid catalyst. Examples of acid catalysts are mineral acids, aliphatic and aromatic sulphonic acids (for example p-toluene sulphonic acid, dinonylnaphthalene sulfonic acid, dodecyl benzene sulfonic acid), copolymers of oxalic acid, maleic acid, hexamic acid, phosphoric acid, polyphosphoric acid, alkyl phosphate esters, ophthalmic acid and acrylic acid. Preferably, acid catalysts are p-toluene sulfonic acid and nitric acid. The amount of catalyst used is typically between 0.01 and 0.2 mol%. This is in contrast to aminoplast-anchored triazines of the prior art described in U.S. Patents. Nos. 5,547,753, 5,612,084 and 5,621,052. The process used there, does not involve a catalytic amount of acid but rather the use of concentrated sulfuric acid as the solvent. It is well known to those with skill in the art that under these conditions, concentrated sulfuric acid is in large excess, and it will be a major self-condensing problem of the amino resins to produce insoluble entangled resin. The reaction is carried out at a temperature from about 20 ° C to 150 ° C, with the maximum temperature depending on the boiling point of the solvent and the pressure employed. Since the reaction involves a series of equilibria, it is convenient that the temperature is above the boiling point of the alcohol that is released during the reaction. In this way, the alcohol is removed by distillation during the course of the reaction, thereby bringing the reaction to completion. THERMOPLASTIC POLYMER COMPOSITIONS The novel compositions of matter described above are useful as ultraviolet (UV) stabilizing additives for polymers, particularly as additives for thermoplastic polymers and thermoset systems. They can be added to the polymer to impart useful stabilizing properties to the polymer by itself or in combination with antioxidants or hindered amine stabilizers. In the stabilization of thermoplastic polymers such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonates, polyurethanes, polyamides and the like, the novel aminoplast anchored stabilizers of the invention are simply incorporated into the thermoplastic materials at a level in the range of about .01 to about 20% by weight by methods known in the art. CURABLE COMPOSITION In thermosetting coating applications, the anchored aminoplast stabilizers of the invention are used to prepare a novel curable composition, this composition is subsequently cured to produce objects and films stable to light. The novel curable composition of the invention comprises: (i) A quantity of effective stabilizer of a stabilizer comprising an aminoplast anchor having more than 0.5 mol of the phenolic stabilizing group per mole of aminoplast elastically connected; (ii) An effective interlacing amount of an entanglement agent; and (iii) .- A material containing polyfunctional active hydrogen. Preferred curable compositions comprise a stabilizer (i), which is a stabilizer of the invention in an amount of at least 0.01% by weight of the total weight of the curable composition. Typically, the novel curable composition of the invention comprises: (i) Approximately .01 to 20% by weight of a novel stabilizer of the invention; (ii) Approximately 3 to 55% by weight of an interlacing agent; and (iii) Approximately 40 to 97% by weight of a material containing polyfunctional active hydrogen. The curable composition may optionally contain a curing catalyst to accelerate curing. The curing catalyst is selected from the group comprising acids, amines, amino group containing resins, organo metal compounds and phosphine. The novel stabilizers of the invention are described above in the section entitled "anchored products". They may be blocked or unblocked, monomeric or oligomeric, or they may be mixtures.

The entanglement agent may be a polyisocyanate or an aminoplast entanglement agent selected from non-esterified aminoplast, partially esterified or fully esterified, or may be any mixture thereof. Aminoplast stabilizers are described above in the section entitled "aminoplast anchors", and include interlayers such as CYMEL MR 1130 resin, CYMEL MR 303 resin, CYMEL MR 1170 resin, POWDERLINK MR 1174 resin, CYMEL MR 1123 resin, and the like. The polyfunctional active hydrogen containing material comprises at least one class of active hydrogen functionality selected from the group consisting of carboxy, hydroxy, amido, mercapto, and a group convertible thereto. Hydroxy and carboxy functional groups are preferred. Especially convenient polyfunctional active hydrogen-containing materials include polyacrylate polyesters, polyurethane polyols, and amine condensation products with epoxy resins, all containing hydroxy groups as reaction sites. The polyesters are obtained in known manner, for example the reaction of polyfunctional carboxylic acids with excess amounts of polyhydric alcohols; the polyacrylates are obtained by the copolymerization of acrylic or methacrylic acid derivatives with hydroxy groups containing derivatives of these acids, such as for example the hydroxyalkyl esters, optionally with the simultaneous use of additional vinyl compounds such as for example styrene. Polyurethanes containing hydroxy groups can be obtained in a known manner, by the reaction of polyisocyanates with excess amounts of compounds containing at least two hydroxy groups. Suitable commercially available hydroxy group-containing polyesters are CYPLEXMR 1531, a polyester of phthalic acid, adipic acid, ethanediol, and tri-methylol propane from Cytec Tndustries, Inc., Cargil Polyester 5776, available from Cargil, and TONEMR 0200 available from Union Carbide Corp. Convenient hydroxy functional acrylic resins are commercially available from SC Johnson & Son, Inc. under the trademark JONCRYLMR 500, a copolymer of styrene hydroxypropyl methacrylate and butyl acrylate, and Rohm & Hass Co. under the brand name AT-400. Also suitable for use are polycaprolactones terminated in hydroxy. The material containing polyfunctional hydroxy functional active hydrogen, comprises compounds and resins selected from acrylic resins, polyester resins, polyurethanes, polyols, products derived from the condensation of epoxy resins with amines and their mixtures. A curing catalyst for accelerating the crosslinking reaction may also be optionally employed however, the curable compositions of the invention may be capable of curing without added catalyst. When a catalyst is present, entanglement is carried out more rapidly at a particular temperature than when a catalyst is not present. Typically, entanglement is performed at a lower temperature with a catalyst present. Acid-curing catalysts usable in the invention include carboxylic acids such as phthalic acid and oxalic acid; sulfonic acids such as paratoluene sulphonic acid, dinonyl naphthalene sulphonic acid, naphthalene sulfonic acid, dodecyl benzene sulfonic acid; phosphoric acids; mineral acids such as nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid and the like. The use of a sulfonic acid is preferred. When employed, the curing catalyst is used in the curable compositions of the invention in effective amounts to accelerate curing at a temperature employed. For example, the catalyst is typically employed in amounts of about .01 to about 2% by weight, with .02 to 1% by weight, based on the weight of curable compositions, preferred. In the practice of the invention, the curable compositions can be adapted for use in solvent-based, water-based and powder-based coating applications. They can also be used in molding applications. Sulfonimide catalysts are particularly well suited for use in powder coating applications. The curable compositions of the invention may also contain other stabilizers such as monomeric or oligomeric hindered amine light stabilizers (HALS), phenolic antioxidants, phosphite antioxidants, sulfur-containing antioxidants, such as sulfides and disulfides, other UV absorbers, scrubbers of acids, fillers or fillers, pigments, pyro-retardants and the like. METHOD OF USE This invention is also an improved method for using the novel annealed aminoplast stabilizers of the invention described above in the section entitled "anchored products". The method uses the novel curable compositions of the invention also described in the section entitled "curable compositions". The novel method disclosed herein is an improved method for coating substrates of the type having the steps of (I) contacting the substrate with a conventional curable composition containing a stabilizer, an entanglement agent and a polyfunctional active hydrogen containing material, and ( II) subsequently curing the conventional curable composition, wherein the improvement comprises: (a) Contacting the substrate with a novel curable composition comprising: (i) An effective stabilizing amount of a stabilizer comprising an aminoplast anchor having more than 0.5 mol of phenolic stabilizing group per mole of aminoplast connected secondarily; (ii) An effective amount of entanglement of an entanglement agent; and (iii) A material containing polyfunctional active hydrogen; and (b) Subsequently curing the novel curable composition. The substrate to be coated can be selected from surfaces such as steel, aluminum, plastic materials and the like. Alternatively, a mole may be used instead of a surface to practice the method of the invention. The contact of a substrate with the novel curable composition of the invention can be carried out by any of the conventional coating methods including spraying, pad applications, brushing, electrostatic spraying or as the case in powder coatings, roller coating application. , curtain coating, dip coating and electro-coating. The curing can be carried out by continuous application of heat at an elevated temperature or at room temperature. Curing can be accelerated by the use of a convenient catalyst such as those employed to cure novel curable compositions. STABILIZED ARTICLES The novel method of using the anchored stabilizers of the invention according to the method described above, generates a product which in this case is an article interleaved in the form of a film such as a coating, or is in the form of an article such as a molded product. The cured compositions can be used as coatings for wire, articles, automotive parts, furniture, pipes, machinery and the like. Arcuately forming surfaces conveniently include plastics, wood, and metals such as steel, aluminum and the like. The cured compositions can also be used to form solid articles such as enclosures, casings, and structural members. The following examples illustrate the preparation and use of the novel stabilizers of the invention by the process of the invention. These examples, however, are not intended to limit the claims in any way. EXAMPLES Examples 1 to 8 The melamine-formaldehyde resins used in these examples, CYMELMR 300 and 303 resins, represent two commercial grades of hexametoxymethyl melamine (HMMM) available from Cytec Industries, Inc. Some physical properties are given in Table I.

Table I. Some physical properties of CYMELMR 300 and 303 resins.

Cymel 300 Cymel 303 Non-volatile > 98% > 98% Viscosity Waxy solid X-Z2 (Gardner-Holt, 25 ° C) Content of 75 58 monomer HMMM, approximately Grade of 1.35 1.7 polymerization These resins are predominantly monomeric HMMMs, but lower levels of dimeric and trimeric analogs that are linked either through methylene, methylene bridges -NCH2N-, or methyleneoxy bridges, -NCH2OCH2N- are also present. For CymelMR 303 resin, the combined methanol or degree of methylation is in the range between 5.1 and 5.3 moles per mole of melamine. The content of methylol, -CH 2 OH, is 1.5-2.0%, and the content of imino, -NH, is very low. Idealized structures representing the 1: 1 adducts of CymelMR 300 and 303 with tris-aryl-1, 3, 5-triazine absorbents of UV BondingPbondable are given in the examples. However, HPLC analyzes indicate that several different species are formed in each reaction. These include substituted mono-, bis-, tris- and higher species, ie melamine "anchors" attached to one, two or three or more chromosome units tris-aryl-1,3,5-triazine. Oligomeric bridged methylene or methyleneoxy species are also present. Example 1: 1: 1 adduct between CvmelMR 300 and 2.4-Bis (2,4-dimethylphenyl) -6- \ 2 -hydroxy-4- (2-hydroxyethoxy) phenyl-1,3,5-triazine (Compound A) Idealized structure of compound A 2, 4 -Bis (2,4-dimethyl-phenyl) -6- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -1,3-triazine (Compound a, 10.0 g , 22.6 mmol) is dissolved in 100 mL of chlorobenzene at 80 ° C.

CymelMR 300 (8.64 g, 22.6 mmoles based on considerable MW of 382) and 0.43 g of para-toluenesulfonic acid (2.3 moles) were added. The solution is stirred at 133-136 ° C for 11 hours. During this time, 2.8 mL of fluid was collected in a Dean-Stark trap. The mixture was then washed with 50 mL of 5% aqueous sodium bicarbonate, 50 mL of water and 50 mL of saturated aqueous sodium chloride. The organic layer was dried over anhydrous potassium carbonate, filtered and concentrated in vacuo resulting in 15.05 g (84% theoretical yield) of compound A as yellow crystal.

Example 2: Adduct 1: 1 between CymelMR 300 Resin and 2,4-Bis (2,4-dimethylphenyl) -6- I "2-hydroxy-4- (6-hydroxyhexyloxy) phenyl-1, 3-5-thiazine (Compound B ) Idealized structure for compound BA a 250 ml round bottom flask equipped with a magnetic stir bar and a distillation head connected to a distillation condenser were charged 20.0 g of 2,4-bis (2,4-dimethylphenyl) -6 - [2-hydroxy-4- (6-hydroxyhexoxy) phenyl] -1, 3-5-triazine (40.0 moles), 15.4 g of CymelMR 300 (40.0 mmoles with low molecular weight) (MW considered 382), 0.60 g of para-toluenesulfonic acid (3.15 mmoles) and 150 mL of toluene. The flask is immersed in an oil bath and the bath temperature is brought to 80 ° C. A vacuum is applied to the system using a water aspirator such that a liquid begins to distill slowly. After collecting 30 mL of distillate in about 3 hours, no starting material was observed by TLC (10% acetone / methylene chloride). The organic layer is extracted with 2 X 200 mL of 0.5 N potassium bicarbonate and dried overnight over magnesium sulfate. Filtration and rotary evaporation, followed by vacuum treatment at 75 ° C for 15 hours, gave 34.2 g of an orange glass (100.3% theoretical yield). The structure was confirmed by NMR ^ H. HPLC analysis showed at least four major peaks containing the tris-aryl-1,3,5-triazine chromophore and essentially no starting material. Example 3: 1: 1 adduct between CymelMR 300 resin and 2,4-bis (2,4-dimethylphenyl) -6-r2-hydroxy-4- (6-carbamoyloxyhexyloxy) phenyl] -1,3-triazine (Compound C ) Idealized structure for the CA compound a 250 ml round bottom flask equipped with magnetic stir bar and distillation head connected to a distillation condenser was charged 20.0 g of 2,4-bis (2,4-dimethylphenyl) -6- [ 2-hydroxy-4- (6-carbamoyloxy-oxy) phenyl] -1, 3-5-triazine (37.0 mol), 14.1 g of Cymel MR 300 (37.0 mmoles based on a MW of 382 considered), 0.60 g of acid for -toluenesulfonic (3.15 moles) and 150 mL of toluene. The flask is immersed in an oil bath and the bath temperature is brought to 74 ° C. A vacuum is applied to the system using a water aspirator, such that a liquid began to distill slowly. After collecting 45 mL of distillate for about 2 hours, no starting material was observed by TLC (10% acetone / methylene chloride). The organic layer is extracted with 2 X 150 mL of 0.5 N potassium bicarbonate diluted with 100 L of methylene chloride and dried overnight over magnesium sulfate. Filtration and rotary evaporation, followed by vacuum treatment at 75 ° C for 15 hours gave 32.4 g of orange glass (98.5% theoretical yield). The structure was confirmed by NMR- ^ ?. HPLC analysis showed at least eight main peaks containing the tris-aryl-1,3,5-triazine chromophore and essentially no starting material.

Step 4: Cvmel adduct MR 300 of Cymel MR 303 resin with 4- \ 4 acid. .6-Bis (2,4-di-ethylphenyl) -1,3,5-triazine-2-ill-3-hydroxyphenoxyacetic. N- (2-hydroxyethyl) amide (Compound D] _ Compound D, idealized structure. A mixture of 370 mg of Cymel MR 303, 500 mg of 4- [4,6-Bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -3-hydroxyphenoxyacetic acid, N- ( 2-hydroxyethyl) amide, and 10 mg of p-TSA is stirred in refluxing toluene for 6 hours. TLC analysis of the reaction mixture revealed that the N- (2-hydroxyethyl) amide starting material was reacted almost completely with the Cymel resin. The product was then isolated by removing toluene in vacuo to give predominantly the 1: 1 adduct. Example 5: 1: 1 adduct of Cymel MR 300 resin with N-2- (2-hydroxyethoxy) ethyl) 4 - 4,6-Bis (2,4-dimethylphenyl) -1,3 -5-triazine-2-acid amide -yl] -3-hydroxyphenoxyacetic acid (Compound E) Compound E, Idealized Structure A mixture of 1.41 g of Cymel MR 300, 2.0 g of 4- [4,6-bis-2,4-dimethylphenyl] -1,3,5-triazine-2-yl] -3- acid hydroxyphenoxyacetic acid, N- (2- (2-hydroxyethoxy) ethyl) amide, and 42 mg of p-TSA is stirred in 100 mL of refluxing toluene for two hours. HPLC analysis of the reaction mixture revealed that the starting material N- (2- (2-hydroxyethoxy) ethyl) amide was completely reacted with the Cymel resin. The mixture was washed with 100 mL of 5% aqueous sodium carbonate and 100 mL water. The organic layer was concentrated in vacuo to give compound E as a yellow glass. HPLC analysis showed four main peaks containing the tris-aryl-1,3,5-triazine chromophore. Example 6: 1: 1 adduct of Cymel 303 resin, with 4-l, 4,6-Bis (2,4-dimethylphenyl) -1,3,5-N-ethyl-N- (2-hydroxyethyl) amide triazine-2-yl-3-hydroxyphenoxyacetic acid (Compound F) Compound F, Idealized Structure A mixture of 363 mg of Cymel MR 300, 500 mg of 4- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -3- acid hydroxyphenoxyacetic acid, N-ethyl-N- (2-hydroxyethyl) amide, and 10 mg of p-TSA is stirred in 10 mL of refluxing toluene. HPLC analysis of the reaction mixture revealed that the starting material N- (2- (2-hydroxyethoxy) ethyl) amide was completely reacted with the Cymel resin. The mixture was washed with 10 mL of 5% aqueous sodium carbonate and 10 mL of water. The organic layer was concentrated in vacuo to give compound F as a pale yellow crystal. HPLC analysis showed at least eight main peaks containing the tris-aryl triazine chromophore. Example 7: 1: 1 adduct of Cymel 303 resin with 2,4-bis (2,4-dimethylphenyl) -6-Y2-hydroxy-4- (acetoacetyloxyethoxy) f-1,3-triazine-triazine Compound G) Compound G, Idealized Structure A mixture of 3.63 g of Cymel MR 300, 5.0 g of 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (acetoacetyloxy) -ethoxy) phenyl] -1 , 3-5-triazine, and 182 mg of p-TSA is stirred in 100 mL in toluene at reflux for 4 hours. HPLC analysis of the reaction mixture revealed that the acetoacetate starting material was completely reacted with the Cymel resin. The mixture was washed with 100 mL of 5% aqueous sodium carbonate and 60 mL of deionized water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo to give compound G as a yellow glass. HPLC analysis showed 10 main peaks containing the chromophore tris-aryl triazine.

Example 8: 1: 1 adduct of Cymel MR 300 resin with 2,4-bis (2,4-dimethylphenyl) -6-Í2-hydroxy-4 - (acetoacetyloxy-hexoxy) phenyl-1,5-triazine (Compound H) 59 Idealized structure D of compound H A mixture of 352 mg of Cymel MR 300, 500 mg of 2,4-bis (2,4-dimethylphenyl) -6 - [2-hydroxy-4 - (acetoacetyl-oxyhexyloxy) phenyl] -1, 3-5-triazine, and 10 mg of p-TSA are stirred in 10 mL of refluxing toluene for 5 hours. HPLC analysis of the reaction mixture revealed that the acetoacetate starting material was almost completely reacted with the Cymel resin. The mixture was washed with 15 mL of 5% aqueous sodium bicarbonate and 15 mL of water. The organic layer was concentrated in vacuo to give a pale yellow glassy solid. HLPC analysis of the product showed nine main peaks containing the tris-aryl-1,3,5-triazine chromophore plus 10.5% acetoacetate starting material (HPLC area% at 290 nm). Example 9: Relative Solubilities in Toluene The solubilities of the tris-aryl-1, 3, 5-triazine Linkable UV absorbers and the corresponding 1: 1 amino resin adducts are summarized in Table II. The data shows how the relatively insoluble triazine-1,3-triazine-triazine UV absorbents become highly soluble by reaction with amino resins. Table II: Solubilities of Triazine UVA's and the corresponding 1: 1 amino resin adducts in toluene at 23 ° C.

Compound Solubility Solubility material of adduct resin split Triazine amino 1: 1 (% in (weight%) weight) a < 1 A > 80 b < 10 B > 80 c < 1 C > 80 d D > 50 e < 1 Compound Solubility Solubility material of adduct resin split Triazine amino 1: 1 (% in (weight%) weight) E 20 f < 10 F 25 g 10 G 20 Compound a is 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -1,3,5-triazine. Compound b is 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (6-hydroxy-oxy) phenyl] -1,3-triazine. Compound c is 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (6-carbamoyloxyhexoxy) phenyl] -1,3,5-triazine Compound d is 4 - [4 , 6-Bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -3-hydroxyphenoxyacetic acid, N- (2-hydroxyethyl) amide The compound e is 4- [4,6-bis] (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -3-hydroxyphenoxyacetic acid, N- (2- (2-hydroxyethoxy) ethyl) amide The compound f is 2,4-bis (2, 4-dimethylphenyl) -6- [2-hydroxy-4- (acetoacetyloxyethoxy) phenyl] -1,3-triazine compound g is 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy] -4- (acetoacetyloxyhexoxi) phenyl] -1,3,5-triazine.

Example 10: Solubility / Compatibility of Compound A A major advantage of melamine / triazine-alkoxy-methylated UV absorbers of the present invention is not only its improved solubility but also its improved compatibility with coating resins compared to the corresponding triazine precursors. For example, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -1,3,5-triazine is only soluble in xylenes in the proportion of about 0.5% Its methoxymethylated melamine adduct, Compound A, on the other hand, has solubility in xylenes greater than 10%. Therefore, compuetso A is much easier to dissolve in high solids coating resin formulations than 2, 4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2 - hydroxyethoxy) phenyl] -1, 3-5-triazine, and overcomes the problem of cratering and poor weather resistance of the final coatings due to the undissolved UV absorbing particles. Example 11: Migration studies in compound B in a fixed thermoplastic acrylic melamine coating system. Compound B is incorporated at a level of 5% in a clear melamine / acrylic coating formulation ((Joncryl 510 / Cymel-303), and the formulation is spread on an aluminum panel.The coating is partially cured at 135 ° C for 10 minutes and a clear top coat (which does not contain UV absorber) is applied. two layers were then cured completely at 135 ° C for 30 minutes.Clinted sections of 10 μm thick thickness were obtained using a micro-tome and each section was analyzed by UV absorbance at 340 nm. sections at depths that correspond to the top layer, whereas a marked increase in absorbance is observed in the sections that are taken at depths corresponding to the second layer. (See figure 1). This shows that little or no UVA migration from the lower layer to the upper layer has occurred during curing.

Distribution pro u aiaaa absor e te ufe; uv in two-layer coatings S17949-28-2A (P 3944-CYMEL linked to UVA) • Depth-micrometer Example 12: Weathering of coating compositions containing Compound A UV Absorbent hydroxy functional triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-hydroxy-ethoxy) phenyl] -1, 3-5-triazine and its amino resin adduct Compound A were formulated in clear acrylic melamine coatings which were applied to steel panels coated E for accelerated weathering test as follows.2.4-Bis (2.4 -dimethylphenyl) -6- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -1, 3-5-triazine (2% based on total solids in resin) is pre-dissolved in a mixture of xylenes and Isopropyl alcohol, and add to the clear acrylic melamine formulation given in Table III. Similarly, Compound A (2.3% based on total resin solids) is pre-dissolved in blends of xylenes and isopropyl alcohol, and added to a separate clear coating formulation. The amount of compound A is adjusted upward to maintain the same moles of UV chromophore of tris-aryl-1,3,5-triazine in both formulations. After an appropriate viscosity adjustment, a clear non-stabilized formulation is sprayed onto pre-coated steel panels with gray ED5000 E-coating and measuring 4 x 12"(ACT Laboratories, Inc. Hillsdale, Michigan Then, the stabilized clear formulations were wet-on-wet coated onto the unstabilized base coat, 3.4 mils were obtained, the light coatings were allowed to evaporate instantaneously for 10 minutes at room temperature. and cured for 30 minutes at 135 ° C. Table III Clear acrylic melamine coating formulation Material Quantity Acrylic Joncryl MR 510 81.25 g CymelMR 303 interlayer 35.0 g Cycat MR 4040 catalyst 1.0 g n-Butanol 20.0 g Xylene 16.0 g Absorbent UVa 2.0 g a) Quantity for 2% based on total resin solids Accelerated weathering was carried out with a QUV device equipped with UVB-313 fluorescent bulbs. A weathering protocol based on ASTM G53 was used (GM cycle): alternate cycles of (i) UV light at 70 ° C for 8 hours and (ii) condensation without UV light at 50 ° C for 4 hours.

Percent glass adhesion and crosslinked adhesion (ASTM D3359) were measured as a function of weathering time. Since E-epoxy coating such as those employed in these panels are known to be particularly sensitive to light, the resistance of clear coatings to delamination is a good measure of the effectiveness of UV absorber. The adhesion test results between processing are summarized in Table IV. Adhesion has a range on a scale of 0 to 5, with 5 the best. Both stabilizers offer improved delamination resistance against an unstabilized coating, but the resin-amino compound Compound A is superior to its hydroxyl functional precursor, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy] -4- (2-hydroxyethoxy) phenyl] -1, 3-5-triazine. In terms of surface properties, Compound A also produces improved gloss retention against 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -1, 3-5-triazine (Table V). Table IV. Effect of Compound A in adhesion of clear coating on an epoxy coating E.

Stabili Exposure hours QV zante 162 438 628 98E None 3 2 0a - - 2.0% at 5 3 - 3 - 2 2.3% A 4- 4 - 4 4 + a) Coating failed.

Compound a is 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -1,3,5-triazine.

Table V. Effect of Compound A on clear coating gloss retention Stabili- Exposure hours QV zante 275 628 985 None 98.6 25% to 2.0% to 97.2 91% 57% 2. 3% A 98.4 91% 74% a) Coating failed Compound a is 2, 4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2-hydroxyethoxy) phenyl] -1, 3-5-triazine.

Claims (17)

1. CLAIMS 1. A composition of matter comprising a monomeric or oligomeric aminoplast anchor with a trisaryl-1,3,3-triazine-linked UV absorber, and represented by the formula: wherein A is an m-functional monomeric or oligomeric aminoplast anchor molecule having at least 0.1 mole of trisaryl-1,3,5-triazine UV absorbers. Linkable per mole of aminoplast anchor bonded through n bridging groups, these groups bridge are chosen from methylene groups and
2. -CHR10- each of R ^ R8 are independently selected from hydrogen, cyano, chloro, bromo, nitro, alkyl with 1 to 24 carbon atoms, aryl with 6 to 24 carbon atoms, aralkyl with 7 to 24 carbon atoms, hydroxy, alkoxy with 1 to 24 carbon atoms and alkyl with 1 to 24 carbon atoms optionally substituted by 1 or more oxygen atoms and / or carbonyl groups, with the proviso that at least one of R ^ R8 is ortho to the point connecting the triazine ring and is a latent hydroxyl or hydroxyl group blocked with an alkyl, phenyl, aryl, acyl, aryl acyl, aminocarbonyl, phosphonyl, sulfonyl or silyl group containing 1 to 18 carbon atoms; X and X 'are independently a direct bond, a straight or branched chain alkylene group with 1 to 24 carbon atoms, a straight or branched chain alkylene group, of 1 to 24 carbon atoms terminated or interrupted by one or more groups selected from -0-, -NH-, -NR9-, -CONH-, -CONR9, one or more carbonyl groups or combinations thereof; And it is a direct II link CONR9-, -Z-CR9-Z 'or -ZN-Z', where Z is -CO-, -C0"M +, -CONR9, -SO- or -S02; and Z 'is -COOR9, -C00"M +, -CHO, -COR9, -CONR9, -CN, -N02, -SOR9, -S02R9, S02OR9 -S02NR29; R9 and R10 independently are selected from the group consisting of hydrogen, linear or branched alkyl with 1 to 24 carbon atoms, aryl with 6 to 24 carbon atoms or aralkyl with 7 to 24 carbon atoms; m is at least 1; and n is at least 0.1. 2. The composition of matter according to claim 1, characterized in that the aminoplast anchor is selected from the group consisting of: 25 polyfunctional carbonates; polyfunctional amides; hydantoins; dialcoxyethylene ureas; Dihydroxy ethylene ureas represented by the formula: homopolymers and copolymers containing carbamate units of the formula: its oligomeric derivatives; and monomeric and oligomeric aminoplastics not etherified or partially etherified, methylolated or partially methylolated in substantially complete form; wherein R9 is hydrogen or a linear or branched alkyl group with 1 to 24 carbon atoms; R11 and R12 are independently hydrogen, alkyl groups with 1 to 24 carbon atoms or aryl groups with 6 to 24 carbon atoms; R 13 is an aliphatic or cycloaliphatic alkyl group with 1 to 24 carbon atoms; an aryl group with 6 to 24 carbon atoms or an aralkyl group with 7 to 24 carbon atoms; and R14 is hydrogen or alkyl with 1 to 24 carbon atoms; and m is at least 1.
3. 3. The composition of matter according to claim 2, characterized in that the aminoplast anchor is a group of the formula: wherein R9 is hydrogen or a linear or branched alkyl group with 1 to 24 carbon atoms.
4. 4. The composition of matter according to claim 2, characterized in that the aminoplast anchor is a group of the formula wherein R9 is hydrogen or a linear or branched alkyl group with 1 to 24 carbon atoms and R11 and R12 independently are hydrogen, alkyl groups with 1 to 24 carbon atoms or aryl groups with 6 to 24 carbon atoms.
5. 5. - The composition of matter according to claim 2, characterized in that the aminoplast anchor is a group of the formula: wherein R9 is hydrogen or a linear or branched alkyl group with 1 to 24 carbon atoms; and R13 is an aliphatic or cycloaliphatic alkyl group with 1 to 24 carbon atoms; an aryl group with 6 to 24 carbon atoms or an aralkyl group with 7 to 24 carbon atoms.
6. 6. - The composition of matter according to claim 2, characterized in that the aminoplast anchor is a group of the formula: wherein R9 is hydrogen or a linear or branched alkyl group with 1 to 24 carbon atoms.
7. 7. - The composition of matter according to claim 1, characterized by the formula: wherein A is an m-functional monomeric or oligomeric aminoplast anchor molecule to which n Trisaryl-1,3,5-triazine linkable UV absorbers are attached through a methylene bond; X, X 'and Y are as described above; R1, R2, R7 independently are chosen from hydrogen, chlorine, cyano, alkyl with 1 to 24 carbon atoms, aryl with 6 to 24 carbon atoms and aralkyl with 7 to 24 carbon atoms; and R9 is alkyl with 1 to 5 carbon atoms.
8. 8. - The composition of matter according to claim 7, characterized in that X and Y are direct links; A is the anchor melamine of the formula and the divalent group -X'- is chosen from: (CH2) p 0a -CH, CH CH, OR15 0a CH2CH CH2Oa- I OR15 wherein 0a denotes the oxygen atom bound to the methylene group of the aminoplast anchor; p is 1 to 24; and R15 is hydrogen or a linear or branched alkyl group with 1 to 24 carbon atoms.
9. 9. - The composition of matter according to claim 7, characterized in that X is a direct bond; A is the anchor melamine of the formula and the divalent group -X'-Y- is chosen from 0a OR R16"(CH2 2) 'p UU (CH2) p Na (CH2) r OR16 wherein 0a and Nb denote the oxygen and nitrogen atoms respectively, attached to the methylene group of the aminoplast anchor; p, q and r each independently are 1 to 24; and R15 and R16 independently are hydrogen or a linear or branched alkyl group with 1 to 24 carbon atoms.
10. 10. The composition of matter according to claim 7, characterized in that X is a direct link; A is the anchor melamine of the formula and the divalent group -X'-Y- is chosen from O (CH2) _ I I Na C CH 2 CH CH 2 OR s Na R 10 -CH, - wherein Na represents the nitrogen atom attached to the methylene group of the aminoplast anchor; and R10 and R15 are as defined above.
11. 11. The composition of matter according to claim 7, characterized in that X is a direct link; A is the anchor melamine of the formula and the divalent group -X '-Y- is chosen from: R9 10 -CH2- CH- -CH2- OR15 15 O 20 OR15 R9 25 OR15 R9 wherein Ca denotes the carbon atom bound to the methylene group of the aminoplast anchor; and R9, R10 and R15 are as defined above.
12. 12. The composition of matter according to claim 2, characterized in that the aminoplast anchor contains a substituent selected from the group consisting of hydrogen, an alkyl or aryl group with 1 to about 20 carbon atoms, or a reactive stabilizing group of the formula -CH 2 OH- or -CH 2 OR 9 wherein R 9 is an alkyl group with 1 to about 20 carbon atoms or another aninated aminoplast anchor group attached by a methylene or a methylene-oxy-methylene joint or a combination of the above groups, provided that , on average, the total number of reactive stabilizing groups for each aminoplast anchor is at least 0.1.
13. 13. The composition of matter according to claim 1, characterized in that the triazine compound on average is substanty reacted with all reactive sites available in the amino resin.
14. 14. The composition of matter according to claim 1, characterized in that the triazine compound on average is reacted with all but one of the reactive sites available in the amino resin.
15. 15. The composition of matter according to claim 1, characterized in that the triazine compound on average is reacted with the amino resin in a porporicon to leave two or more reactive sites available in the amino resin.
16. 16. The composition of matter according to claim 1, characterized in that it also comprises at least 0.1 mol equivalents of a functional UV absorber attached to the aminoplastic anchor, this functional UV absorbent is selected from the group consisting of 2- (2-hydroxyphenyl) -1,3,5-triazines, 2- (2-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, 2-hydroxyoxanilides, salicylic acid derivatives , blocked derivatives thereof and mixtures of any of the foregoing light stabilizing groups.
17. 17. The composition of matter according to claim 12, characterized in that the absorbent of Functional UV is a 2- (2-hydroxyphenyl) benzotriazole, and the mole ratio of functional trisaryl-1,3,5-triazine to functional 2- (2-hydroxyphenyl) benzotriazole is between about 1: 3 to 3: 1.