AN UNSATURATED MELAMINE CONDENSATE, A METHOD OF PREPARING SAME, A HIGH SOLIDS AIR-DRYING COATING COMPOSITION CONTAINING UNSATURATED MELAMINE CONDENSATE AND AN ARTICLE COATED THEREWITH

Abstract: An unsaturated condensate of an alkoxymethylmelamine, an allylic alcohol and an acrylamide wherein the alkoxymethyl group contains from 1 to 4 carbon atoms, wherein the ratio of allylic moieties to acrylamide moieties is in the range of about 3:1 to about 1:3, wherein there is at least about 0.75 allylic moieties and no more than about 3 acrylamide moieties per melamine ring and wherein the total of allylic moieties and acrylamide moieties is in the range of about 2 to about 4 per melamine ring. The unsaturated condensates are used in high solids unsaturated coating systems containing unsaturated oil-modified resins.

Description: AN UNSATURATED MELAMINE CONDENSATE, A METHOD OF PREPARING SAME A HIGH SOLIDS AIR-DRYING COATING COMPOSITION CONTAINING UNSATURATED MELAMINE CONDENSATE AND AN ARTICLE COATED THEREWITH This invention relates to high solids air-drying compositions comprising an unsaturated oil-modified resin of moderate molecular weight and an unsaturated condensate of an alkoxyniethylmelamine, an allylic alcohol and an acrylamide and to a process for the preparation of such condensate. More particularly it is directed to high solids air-drying compositions comprising an unsaturated oil modified resin of moderate molecular weight and an unsaturated condensate of an alkoxymethylmelamine, all alcohol and acrylamide and to a process for the preparation of such condensate. Anti-pollution legislation has caused the coatings industry to seek high solids coatings. Alkyd manufacturers have tried to increase the solids/viscosity ratio of their products by reducing the molecular weight of the alkyd. While this approach has been successful in raising the solids of air dry alkyd paints, it has produced some undesirable side effects in the resulting coatings; namely, lower hardness, solvent resistance and water resistance, and louger tack free and cure times. The use of conventional aminoplast crosslivkers fails to improve these properties in air dry alkyd coatings. The present invention provides an air-drying composition comprising from 50 to 90 parts by weight of an unsaturated civil modified resin and from 10 to 50 parts by weight of an unsaturated melamine condensate. It also provides unsaturated condensates of an alkoxymethylmela- mine, an allylic alcohol and an acrylamide wherein the ratio of allylic moieties to acrylamide moieties is in the range of about 3:1 to about 1:3, wherein there is at least about 0.75 allylic moieties and no more than about 3 acrylamide moieties per melamine ring and wherein the total of allylic moieties and acrylamide moieties is in the range of about 2 to about 4.0 per melamine ring. Another aspect of the invention is directed to a process or the preparatiOn of the condensates which comprises reacting an acrylamide with an alkoxymethylmelamine at a temperature below about 1200 C until the reaction is substantially complete and then reacting the acrylamidealkoxymethylmelamine with an allylic alcohol at a temperature in the range of about 90 to about 110 0C in the presence of a catalytic quantity of an acid catalyst and a polymerization inhibiting quantity of an inhibitor. Still another aspect of the invention is directed to articles coated with the air-drying compositions comprising unsaturated oil-modifle resins and the unsatur- ated melamine condensates. The alkoxymethylmelamine is a methylolated, etherified melamine obtained by reaction of formaldehyde and melamine under conditions well known in the art to minimize the amount of oligomerization which can occur when methylene or methylene ether bridges are formed by intercondensation of methylol groups, followed by etherification with an alcohol or mixture of alcohols. The combined ratio of formaldehyde to melamine in the alkoxymethyimeiaiiiine is in the range of about 5:1 to about 6:1 and the combined ratio of the etherifying alcohol is in the range of about 4.7 to about 6.0 moles per mole of melamine. The etiierifying alcohol is selected from the group consisting of methyl, ethyl and isopropyl alcohols, and mixtures thereof and mixtures with higher alcohols containing up to 10 carbon atoms. However the amount of methoxy, ethoxy or isopropoxy groups should at least be stoichiometric with the allylic alcohol and acrylamide condensing agents to allow ready displacement of alkoxy by the allylic and acrylamide groups. The preferred etherifying alcohol is methyl alcohol because its volatility and low boiling point allow its more ready displacement from the alkoxymethylmelamine. The average degree of oligomerization of the alkoxymethylmelamine is three or less and is preferably less than two. The acrylamide which is condensed with the alkoxymethylmelamine can be represented by the formula: EMI4.1 where Rl and R2 are selected from the group consisting of H and methyl. The preferred acrylamide is acrylamide. The allylic alcohol which is condensed with the alkoxymethylmelamine can be represented by the formula: EMI4.2 where R3 is hydrogen or a C1 tc, C4 alkyl group. The preferred allylic alcohols are allyl alcohol and methallyl. alcohol. The ratio of allylic moieties to acrylamide moieties in the unsaturated melamine condensate is in the range of about 3:1 to about 1:3 so that when the unsaturated melamine condensate is incorporated into unsaturated alkyds it can reduce the viscosity of the system without substantially increasing the time required by the system to reach a tack-free state when it is allowed to d:?y in air. In general the allylic moieties promote a reduction in viscosity of the system, the acrylamide moieties enhance the hardness of the anr-dried coating and the acrylamide and allylnc moieties together enhance the drying properties. There should be at least about 0.75 allylic moieties in the unsaturated melamine condensate and no more than about 3 acrylamide moieties and the total of allylic moieties and acrylamide moieties should be in the range of about 2 to about 4.5 per melamine ring. More preferably the number of allylic moieties per melamine ring is in the range of about 1 to about 3 and the number of acrylamide moieties per melamine ring is in the range nf about 1 to about 2 to provide a balance of viscosity reduction and rate of airdrying to an unsaturated alkyd system and even more preferably the number of allylic moieties is in the range of about 1.5 to about 2.5 and the number of acrylamide moie.ies is in the range of about 1 to about 2. The unsaturated melamine condensate of the present invention can be prepared by the stepwise reaction of the allylic alcohol and the acrylamide or the acrylamide and the allylic alcohol with the alkoxymethylmelamine. Preferably the acrylamide is reacted in a first step with the alkoxymethylmelamine and the allylic alcohol is reacted in a second step. If the allylic alcohol Is reacted in a first step, reaction of the acrylamide in the second step causes some of the allylic alcohol to be displaced by the acrylamide during the reaction, reducing the efficiency of the reaction and tending to form high molecular weight materials. When the acrylamide is reacted in the first step, no displacement of the acrylamide by the allylic alcohol is observed in the second step. An undesirable method of carrying out the reaction is realized when the alkoxymethylmelamine is reacted simultaneously with a mixture of the allylic alcohol and the acrylamide instead of by stepwise reaction. Unexpectedly, an acrylamide byproduct is formed and gelation of the unsaturated melamine tends to occur. In the reaction of the acrylamide with the alkoxymethylmelamine, the temperature is maintained below about 1200C to minimize polymerization reactions and in the initial stage of the reaction the temperature is preferably maintained below about 900C while the methanol generated by the condensation reaction is removed under reduced pressure. In the second stage of the reaction, an excess of allylic alcohol is added to the alkoxymethylmelamine/ acrylamide condensation product and the temperature is gradually increased in the range of about 80 to about 110C while the methanol reaction product is slowly distilled at atmospheric pressure through a multiplate distillation column. When the desired degree of replacement of methyl with allylic groups has occurred the reaction medium is distilled under reduced pressure to remove residual methanol and unreacted allylic alcohol. It is then convenient to add a small quantity of a suitable solvent to the melamine condensate to inhibit a tendency to crystallize which can occur particularly with condensate containing higher levels of acrylamide groups The reaction of the alkoxymethylmelamine and the acrylamide is carried out in the presence of a catalytic amount of on acid catalyst selected from the group consisting of protonic acids of pKa less than about 2 and Lewis acids. A catalytic amount is an amount which allows the reaction to be completed within a reasonable time, usually less than 24 hours at a selected temperature, The catalyst is generally added in an amount of from about 0.1 to about 5 weight percent, preferably from about 0.5 to about 2 weight percent of the reaction mixture. The proton:c acids can be selected from the mineral acids hydrochloric, nitric and sulfuric acids, organic acids such as formic acid and oxalic acid,-and sulfonic acids such as methane sulfonic acid, trifluoromethane sulfonic acid, benzene sulfonic acid and p-toluenesulfonic acid. The sulfonic acids are generally preferred since they are strong acids, readily soluble in the reaction medium and can be readily added wIthout the addition of water. The Lewis acids can be selected from the group consisting of metal halides such as stannic chloride, aluminum chloride, ferric chloride and magnesium bromide, metal alkoxides such as aluminum isopropoxide, tetrapropyl titanate, tetra- butyl ziconate, and diropf diacetonyl titanate, metal salts of organic acids such as stannous octoate, stannic octoate and dibutyl tin diacetate, and boon compounds such as boron trichloride, boron trifluoride and boron trifluoride etherate. For high conversion, boron trifluoride, aluminum chloride and stannic chloride are among the preferred Lewis acids. To prevent premature polymerization of the unsaturated melamine condensate or the acrylamide during the condensation reaction, a polymerization inhibiting quantity of an inhibitor of free radical polymerization is added to the reaction mixutre. Excess of inhibitor should be avoided since it can inhibit the polymerization of air-drying unsaturated oil-modified resins containing the unsaturated melamine condensate of the present invention, causing an excessively long induction period when the compositions are air-dried. Effective inhibitors include slydroquinone, ethers of hydroquinone, and quinone. The unsaturated melamine condensates can be used with unsaturated vehicles to reduce the viscosity of coating systems containing such vehicles, and to improve the drying properties and hardness of the coatings. The condensates are especially useful with air-drying unsaturated or oilmodified resins of molecular weight about lQ,0QG or less and glass transition temperature in the range of about 0 to about 1000C having an oil length in the range of about 15 to about 50%. The oil modified resins can be oil modified alkyd resins prepared from conventional polybasic acids, polyhydric alcohols and oil-modifying fatty acids, or oil-modified styrene allyl alcohol copolymers prepared by esterification of styrene allyl alcohol copolymers containing from about 2 to about 10 hydroxy groups per molecule with oil modifying fatty acid, or oil modified acrylic resins prepared by esterificaion of oil modifying fatty acid and low molecular weight hydroxy containing acrylic. copolymers of glass transition temperature of about 250C or higher prepared by interpolymerization of C4 to C7 7 alkyl acrylates or C5 to C8 alkyl methacrylates with a hydroxy monomer selected from the group consisting of allyl alcohol, methallyl alcohol, and C5 to CQ hydroxy acrylates or Hydroxy methacrylates such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, or oil-modified epoxy resins prepared by reaction of an oil-modifying fatty acid with an epoxy resin condensate of the diglycidyl ether of bisphenol A or an epoxidized polybutadiene. Preferred oil-modified resins are of molecular weight in the range of about 50C to about 800C, and glass transition tem.Der- ature in the range of about 20 to about 60 C and contain an oil modifying fatty acid comprising at least about 60 percent by weigh, of a polyunsaturated fatty acid suc as linoleic or linolenic acid. It is desirable that the oil or fatty acid modifying agent should contain at least 60% by weight, preferably at least 80% by weight, of a polyunsaturated fatty acid such as linoleic acid or linolenic acid, based on the total fatty acid content, Accordingly, the fatty acids which may be used in the present invention are fatty.acids separated from drying oils or semi-drying oils such as dehydrated castor oil fatty acid (a linoleic acid content of 76 to 88%), linseed oil fatty acid (a linoleic acid content of 15% and a linolenic acid content of 52%) and safflower oil fatty acid Ca linoleic acid content of 72 to 80%) as well as linoleic acid, linolenic acid and a mixture of the both. In the preparation of the oil-modified resins it is generally desirable to add a sufficient amount of a polymerization inhibitor such as hydroquinone to inhibit gelation during the reaction. Unsaturated oil modified resin compositions in com- bination with the unsaturated melamine condensates can contain from about 50 to about 90 parts by weight of the unsaturated oil-modified resin and from about 50 to 10 parts by weight of the unsaturated melamine condensate. Preferably the combination contains from about 70 to about 90 parts by weight of the unsaturated oil-modified resin and from about 30 to about 10 parts by weight of unsaturated melamine condensate. Too high levels of the unsaturated melamine condensat can cause longer times to reach a tackfree condition and deterioration of properties such as flexibility in the cured coating especiaily when the con densat contains high levels of acrylamide. When the level is too low no appreciable effect on the viscosity of the coating composition and the hardness and solvent resistance of the coating is obtained. The air-drying conipositions of the present invention comprising unsaturated alkyds and unsaturated melamine condensates may be formulated in any of the conventional solvents for such systems including aromatic hydrocarbons, aliphatic esters, and aliphatic ketones and mixtures thereof and mixtures containing aliphatic hydrocarbons. The solutions can be used at any dilu-tion which is convenient for application of the coating compositions to a substrate. Preferably the solids of the coating compost tions are greater than 50 weight percent and even more preferably 70 percent or greater since advantage can be taken of the ability o the unsaturated melamine condensate to reduce the viscosity of higher molecular weight unsaturated oil-modified resin. The air-drying compositions containing unsaturated oil-modified resins and the unsaturated melamine condensates may be cured at room temperature by means of metal dryers of heavy metals such as cobalt, manganese and zinc salts of naphthenic acid, neodecanoic acid and the like or by means of such metal dryers in combination with the alkali metal salts of these acids. When the coating compositions are used as room-temperature drying paints, they are suitable for painting outdoor structures, and heavy machinery and equipment too bulky to be passed through drying ovens. The unsaturated air-drying compositions may also be force-dried and cured at elevated temperatures of up to about 1000C and more and such cure may be accelerated by conventional free radical catalysts such as peroxides and hydroperoxides and by redox systems such as benzoyl peroxide and dimethirlaniline. The coating compositions can be modified by the addition of pigments, plasticizers, colorants, dyes, pigment dispersing agents, flow control agents, stabIlizers and the like. Other types of unsaturated vehicles which may be usefully combined with the unsaturated melamine condensates are polyesters containing internal unsaturation derived from maleic acid moieties and tha like and pendant unsaturation provided by allylic or acrylic groups. Such poly- ester compositions are conveniently cured by free radical methods at elevated temperatures, and can include signifi- cant amounts of vinyl monomers such as acrylates, metha crylazes and aromatic vinyl monomers such as styrene. The following examples are set forth in illustration of the invention and should not be construed as a limitation thereof. Unless otherwise indicated, all parts and percentages are by weight. EXAMPLE 1 This example describes the preparation of an unsaturated melamine condensate containing 1.5 acrylamide units and 1.5 allyl units per melamine ring. To a kettle equipped with stirrer, thermometer, heating jacket and a vacuum outlet are charged the following: 1024 parts Hexamethoxymethyl melamine 300 parts Acrylamide 3.24 parts Methane sulfonic acid 0.60 parts Hydroquinone (0.2% by wt. on acrylamide) 0.30 parts Quinone (0.1% by wt. on acrylamide) The above are stirred as the temperature is increased to 800C. At 80 C, a vacuum of 380 mm mercury is applied. The temperature and vacuum are slowly increased to 1100C and 50 mm Hg Vac, respectively, until 99 percent of the acrylamide has reacted. This gene rally requires 3 hours from start to finish. At this point, the temperature is reduced, the vacuum outlet is closed and the kettle is connected to a 10 plate Oldershaw fractionation column, and 488 parts allyl alcohol is added to the reaction product. The reaction temperature is gradually increased from 850C to 1020C as 126 parts methanol corresponding to insertion of 1.5 allyl groups per nielamine, is removed. At this point the reaction mixture is neutralized with 50% caustic (NaOH) and the unreacted allyl alcohol and any other volatiles are removed by vacuum distillation at 1100C and 50 mm mercury vacuum. The product is cooled to about 80-850C whereupon 2-butanone (methyl ethyl ketone) is added to produce a 78.4 ó by weight solids product. This product is filtered through a bed of Celite before use. EXAMPLES 2-8 By the procedure of Example 1, the following examples containing different proportions of acrylamido moieties and allyl moieties are prepared from hexamethoxymethylmelamine, acylamide and allyl alcohol. TABLE 1 UNSATURATED MELAMINE CONDENSATES Example Allyl groups Acrylamide groups per melamine ring ner melamine ring 1 1,5 1.5 2 2.5 1.5 3 0.75 1.5 4 2 2 5 0 1.5 6 0 2 7 1 2 8 3 0 EXAMPLE 1A An air-drying resin composition is prepared by blending 1200 parts by weight of a 70 percent xylene solution of an oil modified unsaturated resin (M.W. 60-00, oil length 35), 268 parts of the unsaturated melamine condensate solution of Example 1, 6 parts of a 12% solution of cobalt neo decansate, 12 parts 18% lithium drier sold by Tenneco Inc. under the tradename LTD drier and 32 parts of methyl ethyl ketone. The resulting mixture is stirred until a homogeneous product results. This formulation is 70% by weight total solids and contains an 80/20 w/w solids ratio of oil-modified unsaturated resin to unsaturated melamine condensate. The viscosity of this formulation is 2500 cps &commat; 250C. The coating composition iS applied to 0.64 njn Bonderite 37 steel panels and dried in air. The following procedures are used to evaluate the coating composition: Viscosity is determined by Brookfield Viscometer and Gardner-Holt Viscosity tube comparison at 250C. Formulation stability is determined by storing the formulations in clear Gardner-Holt viscosity tubes and/or in sealed 57 ml. jars (clear) at room temperature. The formulations are exposed to light and are periodically examined for any skin formation and/or viscosity change. Coating thicknesses on steel panels are determined by means of a GE thickness Gage Type B Model h 337AY2.. Tack free times are determined in two ways: A) When the finger with a slight pressure will not leave a mark and the surface is not sticky to the touch. B) A strip of aluminum foil, approx. 19 mm x 76 mm, is smoothed and curled ino a "C" shape by drawing the strip between a flat surface and a glass tube. One end of this curled foil strip is placed on the coating and held in place for 8 seconds with a 17 gram weight. If the foil rolls over when the weight is removed, the coating is judged tack free. Coating hardness is determined by the standard pencil hardness testing procedure (ASTM D3363-74). Solvent Resistance is determined by rubbing a felt tipped marker, the tip of which is saturated with methyl ethyl ketone, over the cured coating and determining the number of rubs necessary to penetrate or dissolve the coating, exposing the bare metal substrate. A single rub constitutes moving the MEK saturated marker across the coating and back over the same path to the starting point. Water spot test. A pool of water, about 12 mm in diameter, is placed on the cured coating and covered ?Jith a watch glass. After 30 minutes at room temperature, the glass cover is removed, the water is removed, d the hard- ness of the exposed portion of the coating is immedIately determined by the standard pencil hardness test described above. Any whitening or other changes in the film appearance (e.g. blistering, swelling, etc.) are also noted. Coating flexibility is determined by means of the Gardner Falling Dart Impact Tester. Failure has occurred when the coating shows any sign of cracking or crazing Durability is determined by exposing coatings on steel substrates to the weatherability cycle of the QUV Accelerated Weathering Tester (Q-Panel Company). Each cycle consists of 8 hours of condensation at 600C followed by 16 hours of ultraviolet at 650C. Data from the evaluation of Example 1A are presented in Table 2. EXAMPLES A-SERIES Air-drying compositions are prepared from the unsaturated melamine condensates of examples 2-6 by the formulation of example 1A to provide a series of coating composi- tions containing unsaturated oil-modified resin and unsaturated melamine condensate in the weight ratio of 80 parts to 20 parts. Data for the evaluation of the coating compositions ere presented in Table 2 along with data for Example 9A comprising the unsaturated resin without the unsaturated melamine condensate. The data show that the mixed unsaturates i.e. the melamine condensates containing both allyl and acrylamide units in Examples 1A, 2A, 3A and 14A cause significant decrease in viscosity of the coating system and improve the hardness, solvent resistance and water resistance of the coatings without adverse effect on the impact resistance and the tack free time while the unsaturates containing only acrylamide units have little effect on hardness, solvent resistance or water resistance and increase the tack free time substantially. Table 2 Evaluation of Air-drying Unsaturated Compositions. A Series Sample Number Example Example Example Example Example Example Example 1A 2A 3A 4A 5A 6A 9A Formulation Appearance hazy 21. hazy hazy hazy sl. hazy sl. hazy clear purple purple purple purple purple purple purple Formulation Visc. (cps) 2400 2300 2500 2400 230 2300 7500 Formulation Shelf Stab. skin 1 day skin 1 day skin 1 day skin 1 day skin 1 day sl. skin skin 1 day sl gel 3wk mod gel 3wk no gel 3wk sl gel 3wk no gel 3wk no gel 3wk no gel 3wk Coating Thickness (mm) .038 .038 .038 .038 .036 .036 .038 Tack Free Time* (min) 110/120 135/145 95/105 105/115 150/230 160/210 75/95 Hardness 1 day 6B- < 6B < 6B < 6B < 6B < 6B < 6B 2-3 days 3B 4B 2B 3B 3B 2B 5B-6B 10 days F- F- F- F- B B B 21 days F F-HB F- F- HB+ HB- B MEK rubs 2-3 days 62 87 48 61 50 45 22 10 days 200 200 120 160 95 75 40 21 days 200 200 160 200 110 95 43 Water Spot 3 days #5B #5B #5B- #5B #4B #4B #6B 10 days #11B- #HB- #B #B- #3B #2B #4B Forward Impact 21 days 1.6 1.3 1.5 1.5 1.0 1.1 1.5 QUV Durability 21 days puples 1 day exposure dense PH dense PH dense PH mod PH few PH few PH No Chg. B with BEUR over BEUR in B with BEUR BEUR fine UR 85% of 2 patches faint UR just noted starting over 75% coating (15% of just start- over most of coating coating) only ing of coating 2 day exposure dense PH dense &num;10 dense &num;10 dense PH Dense &num; 10 Dense Dense &num; 10 and &num;10B BEPH R BER in BER over BER over &num; 10 B+ BER over +R over over 100% 2 patches 100% of 100% of R over 100% of 100% of of coating with PH coating coating 100% of coating coating BER over coating rest of coating * = tack free, test A/test B PH = pinhole B = blistering UR = under rust R = rust EXAMPLES, B-SERIZS Air-drying compositions are prepared from 80:20 blends of the unsaturated oil-modified resin of example 1A and the unsaturated melamine condensates of Examples 1-6 and 8. The compositions contain .07 percent cobalt naphthenate and .045 percent manganese octoate. Coatings are prepared by applying the compositions to Bonderite 37 steel panels and allowing them to air dry. Data for the evaluation of the coatings are presented in Table 3. Taken with the data for the A Series, they show that increasing the allyl level of the unsaturated melamine resin causes a) a decrease in aminoplast and formulation viscosity, b) a decrease in formulation shelf life, and c) an improvement in compatibility of the unsaturated melamine condensate and the unsaturated vehicle. Increasing the acrylamide level of the UMF resin causes a decrease in coating tack free time and flexibility. Decreasing the allyl/acrylamide ratio causes the following properties to go through a maximum: rate of hardness development and final coating hardness, solvent resistance and QUV durability. Table 3 Evaluation of Air-drying. Unsaturated Compositions, B Series Sample Number Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 1B 2B 3B 4B 5B 6B 8B 9B Formulation App. hazy sl. hazy hazy v. hazy hazy sl. hazy clear clear Form. Visc. (cps) 1,900 1,800 2,300 2,300 2,300 2,300 800 7,00 Coating thick. (mm) .033 .033 .033 .036 .033 .028 .028 .033 Tack Free Time* (min) 240/330 42C/ > 600 180/330 226/340 170/300 250/450 400/ > 600 180/330 Hardness 1 day 4B 5B 6B ---- 6B 5B 63-5B 6B 2 days 3B 3B-2B 5B 3B 4B-5B ---- ---- 6B 4 days HB ---- ---- 2B ---- 3B 2B+ 4B 10 days HB HB- B+ B HB- B HB B 21 days F HB B+ HB-F HB B HB B MEK rubs 2 days 25 24 21 20 21 ---- ---- 17 4 days 35 ---- ---- 30 ---- 16 35 22 10 days 70 46 56 50 44 20 45 32 21 days 120 95 95 60 83 37 65 48 Water Spot 21 days B B 2B+ 4B B ---- ---- 3B For. Impact 21 days 1.7 1.6 1.6 1.4 1.8 1.1 1.6 1.8 QUV Durab. 21 days 1 day Exposure Yellow Yellow Yellow Yellow Yellow -Sl- Yellow Med. &num; 10B No chg. UR just sl. UR + UR over starting 100% of coating 2 day Exposure Dense &num; 10 Dense &num; 10 Dense &num; 10 Dull Dense &num; 10 Dense &num; 10 Dense &num; 10 BEUR in BEUR in BEUR over UR over BEUR over BER over BEUR over 3 areas over 4 areas over 15% 85% of 20% of 80% of 25% of: 10% of 15% of of coating coating coating coating coating coating coating 4 day Exposure Dense &num; 9 Similar Dense PH Dense &num; 10 Dense &num; 10 Dense &num; 10 BER in to 2 days; +&num; 10B+ BER over B+R+ + &num; 9B+ BER over 15% of 20% of R over 100% of UR over R over 75% of coating coating 35% coating 95% 100% of coating affected of coating of coating coating EXAMPLES, C SERIES Air-drying compositions similar to Examples lB, 6B and 8B are prepared in which the weight ratio of oilmodified unsaturated resin to unsaturated melamine condensate is 65:35. Coatings are prepared by applying the compositions to Bonderite 37 steel panels and allowing them to air-dry. Data for the evaluation of the coatings are presented in Table 4. They show that the compositions containing high levels of melamine condensate are sub stan- tially lower in viscosity than the unsaturated resin of example 98. However, only the unsaturated melamine condensate containing allyl and acrylamide units (Examples 1B, 1C) gives a significant improvement in hardness and solvent resistance without impairment in tack free time or impact resistance. Indeed Example 1C shows further improvement in solvent resistance and hence crosslink density in comparison with Example 1B. Example 6C, containing the melamine acrylamide condensate shows decreased hardness in comparison with Example 6B and Example 8C containing the melamine allyl alcohol condensate shows a substantial increase in the time necessary to reach a tack free condition. Table 4 Sample Number Example Example Example Example Example Example Example 1B 1C 6B 6C 8B 8C 9B Formulation App. hazy clear sl. hazy sl. hazy clear clear clear Viscosity, cps 1900 950 2300 1000 800 250 7000 Coating Thickness (mm) .030 .033 0.28 .033 .028 .028 .029 Tack free time (min) 270/300 285/360 270/480 285/480 390/ > 600 > 600/ > 24 hr 240/360 Hardness 1 day 2B 3B 6B 6B 5B 5B 5B 4 days HB HB 3B 4B 2B 2B 2B 12 days HB HB B 3B HB HB B 21 days F F B 3B HB HB B MEK rubs 4 days 30 40 16 14 35 33 22 12 days 80 125 20 19 45 60 40 21 days 115 160 37 37 65 67 55 Impact resistance forward, joules 1.6 1.3 1.1 .9 1.6 1.6 1.5 Example 10 An air-drying composition of 70 percent solids is prepared from a solution of an unsaturated oil-modified resin of oil length 32% sold by Cargill under the tradename Alkyd 5700 and the unsaturated melamine condensate of example 1 in a weight ratio of solids of 80:20. The composition contains 0.07 percent cobalt neodecanoate and 0.03 percent LTD drier. The composition is coated on Bonderite 37 steel panels and allowed to air-dry. The coating is evaluated in comparison with a coating prepared from the alkyd resin alone (Example 11). The data are set forth in Table 5. Again the melamine-acrylamide-allyl alcohol condensate in Example 10 improves the coatings hardness, solvent resistance and water resistance without adverse effect on the tack free time and the impact resistance. TABLE 5 Sample Number Example Example 10 11 Compatibility clear clear red-orange orange Viscosity 420 cps 450 cps thin skin 5d. Pot. life Viscosity &commat; 21 days R.T. 480 cps 450 cps Thickness mm. 0.028-.036 0.030-0.033 Appearance Hi gloss Hi gloss colorless colorless Tack Free Time mins.(touch/Al foil) 275/375 225/490 Hardness 0.038 mm. (1 day) CA6B < ¯6B (4 days) 3B 6B (5 days) HB 4B (11 days) HB-F C21 days) HB-F 4B-5B MEX rubs (4 days) 36 16 (11 days) 63 19 - (21 days) 70 17 Water Spot (5 days) #B-2B #6B (11 days) ;2B+ ;6B Forward Tmpact (21 days), joules 1.2 1.2

Claims: WHAT IS CLAIMED IS: 1. An unsaturated condensate of an alkoxymethylmelamine, an allylic alcohol, and an acrylamide wherein the ratio of allylic alcohol moieties to acrylamide mcieties in the condensate is in the range of about 3:1 to about 1:3, wherein the condensate contains at least about 0.75 allylic moieties and no more than about 3 acrylamide moieties per melamine ring and wherein the total of allylic moieties and acrylamide moieties of the condensate is in the range of about 2 to about 4 per melamine ring. 2. The unsaturated condensate of Claim 1, wherein the alkoxymethylmelamine is methoxymethylmelamine. 3. The unsaturated condensate bf Claims 1 or 2, wherein the allylic alcohol is allyl alcohol or methallyl alcohol. 4. The unsaturated condensate of Claims 1 o 2, wherein the allylic alcohol is allyl alcohol. 5. The unsaturated condensate of Claims 3 or 4 wherein the acrylamide is represented by the formula: EMI20.1 wherein R1 and R2 are selected from the group consisting of hydrogen and methyl. 6. The unsaturated condensate of Claim 5, wherein R1 and R2 are hydrogen. 7. An unsaturated condensate of an alkoxymethyl- melamine, allyl alcohol and acrylamide wherein the condensate contains about 1 to about 3 allyl groups and rsi about 1 to about 2 acrylamldo groups per melamine ring. 8. The unsaturated condensate of Claim 7, wherein the alkoxymethylmenamine is a methoxymethylmelamine. 9. An unsaturated condensate of an dlkoxymethylmelamine, allyl alcohol, and acrylamide wherein the condensate contains about 1.5 to about 2.5 allyl moieties and about 1 to about 2 acrylamide moieties per melamine ring. 10. The unsaturated condensate of Claim 9, wherein the alkoxymethylmelamine is a methoxymethylmela- mine. 11. A process for the preparation of an unsaturated condensate of an alkoxymethylmelamine, an allylic alcohol, and an acrylamide which comprises reacting the acrylamide with the alkoxymethylmelamine at a temperature below about 120 C until the reaction is substantially complete and reacting the acrylamide - alkoxymethyl melamine condensate with the allylic alcohol at a temperature in the range of about 80 to about 110 C. in the presence of a catalytic quantity of an acid catalyst and a polymerization-inhibiting quantity of an inhibitor. 12. The process of Claim ll, wherein the condensate has a ratio of & lylic moieties to acrylamide moieties in the range of about 3:1 to about 1:3, the total of allylic moieties and acrylamide moieties being in the range of about 2 to about 4.0 per melamine ring, at least 0.75 being allylic moieties and not more than 3 being acrylamide moieties. 13. The process of Claim 12, wherein the alkoxymethylmelamine is a methoxymethyltnelamine, the allylic alcohol is allyl alcohol and the acrylamide is acrylamide. 14. The process of Claims 11, 12, or 13, wherein the catalyst is an acid of pKa less than about 3. 15. An air-drying composition comprising about 10 to aDout 50 parts by weight of the unsaturated condensate of any Claims 1-10 and about 90 to about 50 parts by weight of an unsaturated oil-modified resin. 16. The air-drying composition of Claim 15 wherein the unsaturated oil-modified resin is selected from ehe group consisting of oil-modified alkyd resins, oil-modified styrene allyl alcohol copolymers, oil-modi fied acrylic resins and oil-modified epoxy resins of molecular weight up to about 10,000 and glass transition temperature in the range of about 0 to about 100 0C, having an oil length in the range of about 15 to about 50%. 17. The air-drying composition of Claim 16 wherein the molecular weight of the unsaturated oil-modified resin is in the range of about 500 to about 8000 and the glass transition temperature is in the range of about 20 to about 600C. 18. An article coated with any of the air-drying compositions of Claims 15-17.

Inventors: LE BLANC, JOHN ROGER, SANTER, JAMES OWEN, STRAZIK, WILLIAM FRANCIS
Applicants: MONSANTO COMPANY
Application year: 1980
Main classification: C08G12
IPC codes: C09D167, C09D161, C08G12, C09D4