A process for preparation of room-temperature curable resins

Abstract: Described is a process for the preparation of room-­ temperature curable resins which comprises reacting a compound (A) containing at least two acryloyl groups and/or methacryloyl groups, and having a number-average molecular weight from 100 to 100,000 with an aminosilane compound (B) under substantially water-free conditions,and subsequently reacting the reaction product of the aminosilane-modified resin with a monofunctional isocyanate.

Description: The present invention relates to a process for the production of room-temperature curable resins having a hydrolyzable silyl group as a terminal group. More particularly it provides room-temperature curable resins which are excellent in flexibility, solvent resistance and adhesive properties to organic substances, and are useful as a base resin for coatings, adhesives, pressure-sensitive adhesives, sealing agents, and potting agents, and further as a blend with cellulose of nitrocellulose, cellulose acetate butyrate, and with polyester, alkyd, and acryl, and in addition as a blend resin with a vinyl resin containing a hydrolyzable silyl group (for example, refer to Japanese Patent Application (OPI) No. 54-36395) (a term (OPI) herein means unexamined Japanese Patent Application). In US-A-4 429 082 there are described filmforming resins and coating compositions containing the filmforming resins. The filmforming resins are formed from the reaction of an intermediate and an aminosilane. The intermediate has a nonvinyl addition backbone which is formed by a condensation reaction and has at least two amine reactive acrylylresidues per molecule. The resins are ungelled and essentially acrylylfree. In US-A-4 430 486 there are described filmforming resins and coating compositions containing the filmforming resins. The filmforming resins are formed from the reaction of a urethane resin and an aminosilane. The urethane resin has an average of greater than 1 amine reactive acrylylresidue per molecule and a free isocyanate content of up to about 15 %. The resins are ungelled and have an acrylylcontent of from about 0.2 - about 2 milli-equivalents per gram. In EP-A-0 149 741 there is described a liquid radiation - curable coating composition which is adapted to deposit, after radiation curing, an adherent cured coating on a glass surface. The composition comprises a radiation - curable polyethylenic polymeric organic compound and a polyalkoxysilane containing an organic substituent which carries a single active hydrogene atom which is capable of reacting with ethylenic unsaturation by Michael Reduction. The present inventors found that aminosilane-modified resin can provide a curable resin excellent in room-temperature curable properties, flexibility, solvent resistance, and adhesiveness to organic substances, and they filed a patent application (Japanese Patent Application (OPI) No. 60-197733) with the Japanese Patent Office. Aminosilane-modified resin, however, is not necessarily satisfactory, in spite of the aforesaid features, in points of weather caused yellow-discoloration and shelf-stability (particularly in case of water contamination). The present inventors continued their assiduous study to improve the aforesaid undesirable properties, and found that the weather caused yellow-discoloration and shelf-stability can be improved to a great extent by capping the active hydrogen of an amino group of aminosilane-modified resin with a monofunctional isocyanate compound to introduce N,N,N'-trisubstituted urea, without deteriorating the effects of flexibility, solvent resistance, and adhesiveness to organic substances, and they have accomplished the present invention. Even though a room-temperature curable resin according to the present invention contains a urea group having a high aggregation property, the resin is characterized by showing a low viscosity and having high compatibility with other resins. Since a polyester resin containing a hydrolyzable silyl group as disclosed in Japanese Patent Publication No. 30711/71 contains in a main chain a N,N'-disubstituted urea group having a high aggregation property, the polyester resin is expected to be improved in both flexibility and solvent resistance. However, it is assumed that due to the high aggregation property of the N,N'-disubstituted urea group in a main chain, the polyester resin shows a drawback such as high viscosity and low compatibility with other resins. The room-temperature curable resins of the present invention may effectively be used in view of their room-temperature curability and high solvent resistance as a paint component for repairing an automobile body, and in view of their low viscosity as a so called high solidification paint for coating new automobiles which is earnestly required. Accordingly the present invention provides a process for the preparation of room-temperature curable resins which comprises reacting a compound (A) containing at least two acryloyl groups and/or methacryloyl groups (hereinafter referred to as (meth)acryloyl groups) and having a number-average molecular weight from 100 to 100,000 with an aminosilane compound (B) of the general formula (wherein X is a hydrolyzable group selected from the group consisting of halogen, alkoxy, acryloxy, ketoiymate, amino, acid amide, aminoxy, mercapto, alkenyloxy groups; R₁ is a C₁ - C₁₀ alkyl group, aryl group, or aralkyl group; R₂ is a C₁ - C₁₀ bivalent alkyl group, aryl group, or aralkyl group; n is an integer of 1 to 3, m is an integer of 1 to 10), at a ratio of at least 0.2 equivalents of primary amino groups contained in the compound (B) to one equivalent of (meth)acryloyl groups contained in the compound (A), and under substantially water-free conditions, subsequently reacting the reaction product of the aminosilane-modified resin with a monofunctional isocyanate compound (C) of the general formula R₃ - NCO (wherein R₃ is a C₁ - C₂₅ alkyl group, aryl group, aralkyl group, at a ratio of 0.9-1.5 equivalents to one equivalent of active hydrogen of amino groups contained in the aminosilane-modified resin, and under substantially water-free conditions to obtain a room-temperature curable resin having an amine value of 2 mg KOH or lower. As (meth)acryloyl-group-containing compound (A) employed in the present invention, there is no particular restriction, so long as it is a compound containing at least two (meth)acryloyl groups in a molecule, and having 100 - 100,000 of number-average molecular weight. As typical examples, the following compounds may be included: (1) Polyfunctional (meth)acrylates, such as ethylene glycol-di(meth)acrylate, trimethylolpropane-tri(meth) acrylate, (2) polyester-(meth)acrylates obtained by polycondensation of polyalcohols, such as ethylene glycol, propylene glycol, glycerin, trimethylol, propane, with polyfunctional carboxylic acids, such as phthalic acid, trimellitic acid, and (meth)acrylic acid; (as such polyester (meth)acrylate, there are, for example, ARONIX® M-6100, M-6200, M 6400X, M 6420X, M-6300, M-7100, M 8030, M-8100, produced by Toagosei Chemical Industry Co., Ltd.), (3) polyurethane(meth)acrylate obtained by addition of a hydroxyl-group-containing (meth)acrylate, such as 2-hydroxyethyl(meth)acrylate to a polyfunctional isocyanate compound, such as tolylene-diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene-diisocyanate, xylene-diisocyanate, isophorone-diisocyanate, (4) polyurethane(meth)acrylate obtained by addition of a hydroxyl-group-containing (meth)acrylate, such as 2-hydroxy(meth)acrylate, to an isocyanate-group-containing polyurethane resin which is obtained by polyaddition of a polyalcohol, such as ethylene glycol, trimethylolpropane, a polyester polyol, a polyether polyol, to a polyfunctional isocyanate, such as tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene-diisocyanate, xylene-diisocyanate, isophorone-diisocyanate, (as such polyurethane(meth)acrylates, for example, ARONIX® M-1100, M-1200, products of Toagosei Chemical Industry Co., Ltd., and VISCOTE® 813 and 823, products of Osaka Organic Chemistry Co., Ltd. may be mentioned). (5) polyesterurethane-(meth)acrylate obtained by addition of hydroxyl-group-containing polyester (meth)acrylate (for example, Placcel® FM-1, FM-4, FM-8, FA-1, FA-4, FA-8, products of Daisel Ltd., and TONE M-100, a product of Union Carbide Corp.) obtained by ring-opening polymerization of ε-caprolactone in the presence of hydroxyl-group-containing (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, and catalysts, such as an organic titanate, tintetrachloride, or perchloric acid, to a polyfunctional isocyanate compound such as tolylene-diisocyanate diphenylmethane-4,4'-diisocyanate, hexamethylene-diisocyanate, xylylene-diisocyanate, isophorone diisocyanate, (6) polyesterurethane-(meth)acrylate which is obtained by addition of hydroxyl-group-containing polyester-(meth)acrylate to isocyanate-group-containing-polyurethane resin obtained by polyaddition of a polyalcohol , such as ethylene glycol, dimethylolpropionic acid, 1,10-decane diol, trimethylolpropane, a polyether polyol, a polycaprolactone (for example, Placcel® 205k 212, 220, 308, 312, 320, 212 AL, 220 N, 220 AL, products of Daisel Ltd.) or alcohol-modified silicone oil (for example, F-99-199®, F-99-258®, products of Japan Unicar Co., Ltd.) to polyfunctional isocyanate, such as tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, (7) polyether(meth)acrylate (for example, 14 EG-A®, product of Kyoeisha Yushi Co., Ltd.) obtained by condensation of polyethylene glycol, or polypropylene glycol and (meth)acrylic acid, (8) epoxy(meth)acrylate (for example, VISCOTE® 540, product of Osaka Organic Chemistry Co., Ltd.) obtained by reacting an epoxy resin, (for example, EPICOTE® 828, product of Yuka Shell Co., Ltd.) With (meth)acrylic acid, or a hydroxyl-group-containing (meth)acrylate, and (9) silicone (meth)acrylate obtained by condensating silanol-group-containing silicone oil and (meth)acrylate containing a hydrolyzable-silyl-group, such as γ-(meth)acryloxy-propyltrimethoxysilane. If the compound (A) is required to be improved in an aggregation property to a room-temperature curable resin, a polyurethane acrylate is preferably used. As compounds (B) employed in the present invention, there are aminosilane compounds, such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, H₂NCH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂Si(OMe)₃, H₂NCH₂CH₂NHCH₂CH₂NHCH₂CH₂CH₂Si(OEt)₃. And further, some mercaptosilane compounds, such as γ-mercaptopropyltrimethoxysilane may also be employed combinedly. In order to obtain a desired aminosilane-modified resin from (meth)acryloyl-group-containing compounds (A) and an aminosilane compound (B), (A) and (B) are mixed to be reacted substantially under water-free conditions, at a temperature of from normal temperature to 200°C. This reaction is a so-called "Michael Addition," and if it is desired to employ only primary amines selectively for the reaction, it is preferable to add compound (A) to compound (B). And for the purpose of inhibiting radical polymerization in the reaction of a (meth)acryloyl group of compound (A), it is preferable that polymerization inhibitors, such as hydroquinone, benzoquinone, 2,5-di-t-butylbenzoquinone, phenothiazine, hydroquinone-monomethylether and 2,6-di-t-butyl-4-methylphenol (BHT) be added prior to the reaction. Among the above polymerization inhibitors hydroquinone-monomethylether or BHT is preferable in view of the tinting. The reaction proceeds even without catalysts, but catalysts to promote the addition reaction may also be employed, and as such catalysts may be mentioned, for example, tertiary amines, such as dimethylbenzylamine, 2,4,6-tris(dimethylaminoethyl)phenol, quaternary ammonium salts, such as benzyl-trimethylammonium hydroxide, and alkalis, such as sodium methoxide. The ratio of component (B) to component (A) in the reaction is from 0.2 to 20, preferably from 0.8 to 10 equivalents of primary amino group contained in compound (B) per equivalent of (meth)acryloyl group contained in compound (A). If the equivalent ratio is less than 0.2, the effects of the present invention, for example, the effect of improving adhesiveness to organic substances will be small. And if the above ratio exceeds 20 equivalents, it is undesirable in view of the cost, although no problem is caused thereby in the process of synthesis or in the properties of the resin. In carrying out the reaction, use of solvents is unnecessary, but if it facilitates the reaction, solvents may also be used. And as such solvents, toluene, xylene, butyl acetate may be included. As monofunctional isocyanates (C) to be reacted with amino groups of the aminosilane-modified resin obtained in the reaction, the following compounds may be mentioned specifically; methyl isocyanate, ethyl isocyanate, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, stearyl isocyanate, γ-isocyanate-propyltriethoxysilane, γ-isocyanate-propyltrimethoxysilane. The reaction proceeds readily accompanied by exothermic heat just by adding a monofunctional isocyanate (C) to an aminosilane-modified resin or a solution thereof at a temperature of from ordinary temperature, for example, room-temperature, to 60°C. The ratio of the reaction component (C) in the reaction is from 0.9 to 1.5, preferably from 0.95 to 1.2 equivalents, per equivalent of active hydrogen of amino group of aminosilane-modified resin. If the equivalent ratio is less than 0.9, the effect of improving the stability will be small, and if it exceeds 1.5, it is undesirable, because monofunctional isocyanate will remain as excess in the system. An amine value of the room-temperature curable resin (solids-content concentration, 10.0%) thus obtained, is required to be 2 or less, preferably 1 or less. When the amine value will be over 2, the resin shows less stability, thereby being liable to gelate. The amine value is obtained by the following equation with a result of neutralization titration. wherein A represents a consumption of a 0.2N ethanol hydrochloric acid solution in ml; f represents potencies of the 0.2N ethanol hydrochloric acid solution; and S represents the amount of the sample in g. For stabilization of the room-temperature curable resin according to the present invention, the following compounds may be employed: hydrolyzable esters of methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyltrimethoxysilane, methylsilicate, ethylsilicate, methyltrimethoxysilane, partially hydrolyzed methylsilicate, partially hydrolyzed methyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane; and alcohols, such as methanol, ethanol, isopropyl alcohol, butyl alcohol. For setting the room-temperature curable resin obtained according to the present invention, the following curing catalysts may be employed: alkyltitanates, organo aluminum compounds, acid compounds, such as phosphoric acid, phosphoric ester p-toluenesulfonic acid; amines, such as ethylene diamine, tetra-ethylenepentamine; organo-tin compounds such as dibutyltin-dilaurate, dioctyltin maleate; and basic compounds, such as sodium hydroxide and sodium methylate. The amount of the curing catalyst to be used is from 0.005 to 10, preferably from 0.1 to 8 parts by weight per 100 parts by weight of the room-temperature curable resin. The thus obtained room-temperature curable resin is improved, as compared with aminosilane-modified resin, in resistance to weather caused yellow-discoloration, stability (particularly in case of water contamination), and further in solvent resistance due to the N,N,N'-trisubstituted urea bonds formed in side chains. And as compared with the case of having N,N'-disubstituted urea bonds in the main chain, the room-temperature curable resin has a low viscosity, and a good compatibility with other resins. The curable resin prepared according to the present invention has a hydrolyzable silyl group as its end group, and is characterized with excellent properties of room-temperature curing, flexibility, solvent resistance, adhesiveness to organic substances, and compatibility. Accordingly, it is useful as a base resin for coatings, adhesives, pressure-sensitive adhesives, sealing agents, potting agents, and as a blend with polyesters, alkyd resins, acryl or epoxide resins, cellulose or nitrocellulose, cellulose acetate butyrate, and further as a blending resin for hydrolyzable-silyl-group containing vinyl resins(refer, for example, to Japanese Patent Application (OPI) No. 36395/79). The present invention is illustrated more specifically with reference to the following examples. Example 1 A reactor which is equipped with an agitator, a thermometer, a nitrogen-introduction pipe, a dropping funnel and a cooling pipe was charged with 123.3 g of γ-aminopropyl-triethoxysilane, 75.9 g of γ-mercaptopropyl-trimethoxysilane and 100 g of xylene, subsequently 361.3 g of ARONIX® M6200 (bifunctional oligoesteracrylate, Mn 680, product of Toagosei Chemical Co., Ltd.) was added droppedwise in a nitrogen atmosphere at a temperature of 30°C over a period of one hour, then the reaction was continued at a temperature of 60°C for another hour. The reactor was cooled down to a temperature of 20°C to give an aminosilane-modified resin. Infrared absorption characteristics were examined on the above obtained silane-modified resin, and a complete disappearance of the absorption at 1630, 1410 cm-1 of the acryloyl group was observed. Further in the reactor 39.6 g of ethylisocyanate was added dropwise at a temperature of 20°C, and reacted further at a temperature of 60°C for 30 minutes, subsequently 300 g of xylene was added thereto to give the curable resin 1 (solids-content concentration, 60%). In the curable resin, the infrared absorption at 1640 cm⁻¹ of the urea bond was observed, and its number-average molecular weight calculated by GPC method was 1100, and its amine value was 0.4. Example 2 A reactor which was equipped with an agitator, a thermometer, a nitrogen-introduction pipe and a cooling pipe was charged with 50.8 g of hexamethylene-diisocyanate, 346.0 g of Placcel® FA 4 (polycaprolactone containing acryloyl groups at both ends, Mn 572, product of Daisel Ltd.) and 100 g of xylene, then the reaction was carried out under agitation in a nitrogen gas atmosphere, at a temperature of 90°C for 2 hours to give a polyester-urethane which contains acryloyl groups at both ends (wherein the infrared absorption at 2270 cm⁻¹ of NCO had disappeared, but the absorption at 1630 to 40⁻¹ of the acryloyl group remained). Another reactor which was equipped with an agitator, a thermometer, a nitrogen-introduction pipe, a dropping funnel and a cooling pipe was charged with 140.3 g of γ-aminopropyltriethoxysilane, and the polyesterurethane which contains acryloyl groups at both ends was added thereto continuously under agitation, in a nitrogen gas atmosphere, at a temperature of 30°C over a period of one hour, and reacted at a temperature of 60°C for another hour to give an aminosilane-modified resin. As the result of the examination of thus obtained resin, the infrared absorption at 1630, 1410 cm⁻¹ of the acryloyl group had disappeared. And further, 62.9 g of butyl isocyanate was added dropwise in the reactor at a temperature of 20°C, and reacted at a temperature of 60°C for 30 minutes, subsequently 300 g of xylene was added thereto to give curable resin 2 (solids-content concentration, 60%). In the obtained curable resin, the infrared absorption at 1640 cm⁻¹ was observed, and its number-average molecular weight by GPC method was 1800, and its amine value was 0.5. Example 3 A reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe and a cooling pipe was charged with 75.8 g of isophorne-diisocyanate (IPDI), 209.5 g of Placcel® 212 AL (polycaprolactone containing hydroxyl groups at both ends, Mn 1260, product of Daisel Ltd.), and 100 g of xylene, and reacted under agitation, in a nitrogen gas atmosphere, at a temperature of 110°C for 2 hours, subsequently 195.2 g of Placcel® FA-4 was added thereto and reacted further at a temperature of 100°C for another 2 hours to give polyester-urethane which contains acryloyl groups at both ends (wherein the infrared absorption at 2270 cm⁻¹ of NCO had disappeared, but absorption of 1630 to 40 cm⁻¹ by acryloyl group remained). Another reactor which was equipped with an agitator, a thermometer, a nitrogen-introduction pipe, a dropping funnel and a cooling pipe was charged with 82.6 g of γ-aminopropyltriethoxysilane, and the above obtained polyesterurethane which contains acryloyl groups at both ends was continuously added thereto, under agitation and in a nitrogen atmosphere at a temperature of 20°C over a period of one hour, and reacted further at a temperature of 60°C for another hour to give aminosilane-modified resin. In the obtained resin, the infrared absorption at 1630, 1410 cm⁻¹ of the acryloyl group had disappeared. Further, 37.1 g of butyl isocyanate was dropped in the reactor at a temperature of 20°C, and was reacted at a temperature of 60°C for 30 minutes, subsequently 300 g of xylene was added thereto to give curable resin 3 (solids-content concentration, 60%). In the obtained curable resin, the infrared absorption at 1640 cm⁻¹ of the urea bond was observed, and its number-average molecular weight by GPC method was 3500 and its amine value was 0.1. Example 4 A reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe and a cooling pipe was charged with 114.4 g of F-99-199® (alcohol-modified silicone oil, Mn 540, product of Japan Unicar Co., Ltd.), 94.1 g of IPDI and 100 g of xylene, which were reacted with one another under agitation, in a nitrogen atmosphere, at a temperature of 120°C for 2 hours, and further thereto 242.4 g of Placcel® FA-4 ( Mn 572) was added, and reacted further at a temperature of 100°C for another 2 hours to give silicone-polyester which contains acryloyl groups at both ends. In the spectrum examination of the above obtained prepolymer, the infrared absorption at 2270 cm⁻¹ of the NCO had completely disappeared, but the absorption at 1630 to 40 cm⁻¹ of the acryloyl group had remained. Then another reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe, a cooling pipe and a dropping funnel was charged with 103 g of γ-aminopropyl-triethoxysilane, subsequently the above obtained silicone-polyester which contains acryloyl groups at both ends was added dropwise thereto at a temperature of 30°C over a period of 2 hours, and further reacted at a temperature of 60°C for one hour. After it was cooled down to 20°C, 46.1 g of butyl isocyanate was added dropwise thereto at a temperature of 60°C for 30 minutes, subsequently 300 g of xylene was added thereto to give curable resin 4 (solids-content concentration, 60%). In the above obtained curable resin, the infrared absorption at 1640 cm⁻¹ of the urea bond was observed, and its number-average molecular weight by GPC method was 3000 and its amine value was 0.2. Example 5 An aminosilane-modified resin was prepared according to the same manner as disclosed in Example 3. A curable resin 5 (solids-content concentration, 60%) was obtained according to the process disclosed in Example 3 except that 96.3 g γ-isocyanate propyltriethoxysilane was used in place of 37.1 g of butyl isocyanate and 33.9 g of xylene was added in place of 300 g thereof. In the obtained curable resin, the infrared absorption at 1640 cm₋¹ of the urea bond was observed, and its number-average molecular weight by GPC method was 3800 and its amine value was 0.1. Example 6 A reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe, a cooling pipe and a dropping funnel was charged with 84.8 g of isophorone-diisocyanate (IPDI), 251.6 g of polypropylene glycol, Mn 993, and 100 g of xylene, and reacted under agitation, in a nitrogen gas atmosphere at a temperature of 120°C for 5 hours, subsequently 161.6 g of Placcel® FA-4 was added thereto and reacted further at a temperature of 90°C for another 2 hours to obtain polyether ester urethane which contains acryloyl groups at both ends. Another reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe, a cooling pipe and a dropping funnel was charged with 65.4 g of γ-aminopropyltriethoxysilane and the above obtained polyether ester urethane which contains acryloyl groups at both ends was continuously added thereto under agitation and in a nitrogen atmosphere at a temperature of 20°C for a period one hour, and reacted further at a temperature of 60°C for another one hour to obtain aminosilane-modified resin. Further, 37.0 g of cyclohexyl isocyanate was dropped in the reactor at a temperature or 20°C, and was further reacted at a temperature of 60°C for 30 minutes, subsequently 300 g of xylene was added thereto to give curable resin 6 (solids-content concentration, 60%). In the obtained curable resin, the infrared absorption at 1640 cm⁻¹ of the urea bond was observed, and its number-average molecular weight by GPC method was 4500, and its amine value was 0.15. Comparative Example 1 A reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe and a cooling pipe was charged with 50.8 g of hexamethylene diisocyanate, 346.0 g of Placcel® FA-A, and 100 g of xylene, and they were reacted under agitation, in a nitrogen gas atmosphere at a temperature of 90°C for 2 hours to give polyurethane which contains acryloyl groups at both ends (although the infrared absorption at 2270 cm⁻¹ of the NCO thereof had disappeared, the absorption at 1630 to 40 cm⁻¹ of the acryloyl group remained). Another reactor which was equipped with an agitator, a thermometer, a nitrogen-introduction pipe, a dropping funnel and a cooling pipe was charged with 140.3 g of γ-aminopropyltriethoxysilane, and the obtained polyester-urethane which contains acryloyl groups at both ends was continuously added thereto under agitation in a nitrogen gas atmosphere at a temperature of 30°C over a period of one hour, and further reacted at a temperature of 60°C for another hour followed by addition of 258.1 g of xylene to give aminosilane-modified resin (solids-content concentration, 60%). In the obtained aminosilane-modified resin, the infrared absorption at 1410 cm⁻¹ of the acryloyl group had disappeared, and its number-average molecular weight by GPC method was 1700 and its amine value was 66. Naught point five (0.5) parts of dibutyltin-dilaurate was added to 100 parts by weight (solids-content concentration, 60%) of a solution of each of the curable resins obtained in the Examples 1-6, and in the Comparative Example 1, and the solution was diluted to an appropriate viscosity for painting, subsequently it was sprayed respectively on abrased (#400) amilac white enamel (melamine alkyd resin paing, product of Kansai Paint Co., Ltd., backed at 130°C for 30 minutes), and on a polyethylene sheet to form a 60 µm thick film. Each sample was left to stand at normal temperatures for 7 days, and then the physical properties thereof were determined, the results are shown in the table below. Example 7 A reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe and a cooling pipe was charged with 92.0 g of isophorone-diisocyanate (IPDI), 212.8 g of Placcel® FA-1 (polycaprolactone containing acryloyl groups at both ends, Mn 230), 0.5 g of 2,6-di-t-butyl-4-methylphenol (BHT) and 100 g of xylene, then the reaction was carried out under agitation in a nitrogen gas atmosphere, at a temperature of 90°C for 2 hours to obtain polyester-urethane which contains acryloyl groups at both ends (wherein the infrared absorption at 2270 cm⁻¹ had disappeared, but the absorption at 1630 to 40 cm⁻¹ had remained). Another reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe, a dropping funnel and a cooling pipe was charged with 173.8 g of γ-aminopropyltrimethoxysilane, and the polyester-urethane which contains acryloyl groups at both ends was added thereto continuously under agitation, in a nitrogen gas atmosphere, at a temperature of 20°C over a period of one hour, and reacted at a temperature of 60°C for another hour to give aminosilane-modified resin. As the result of examination of the thus obtained resin, the infrared absorption at 1630, 1410 cm⁻¹ of the acryloyl group had disappeared. And further, 121.4 g of cyclohexyl isocyanate was added dropwise in the reactor at a temperature of 20°C, and reacted at a temperature of 60°C for 30 minutes, subsequently 228 g of xylene, 60 g of isopropylalcohol, and 12 g of orthomethylacetate were added thereto to give curable resin 6 (solid-content concentration, 60%). The viscosity of the curable resin solution, thus obtained, was 50 cps at 23°C. In the obtained curable resin, the infrared absorption at 1640 cm⁻¹ was observed, its number-average molecular weight by GPC method was 1300, and its amine value was 0.1 Comparative Example 2 A reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe and a cooling pipe was charged with 206.6 g of isophorone-diisocyanate (IPDI), 218.6 g of Placcel® 205 (polycaprolactone containing hydroxyl groups at both ends, Mn 470), and 100 g of xylene, and reacted under agitation, in a nitrogen gas atmosphere, at a temperature of 90°C for 2 hours to obtain polyester-urethane which contains isocyanate groups at both ends. In the obtained polyester-urethane, with an isocyanate titration according to the di-butylamine method it was recognized that 50% isocyanate remained in the isophorone-diisocyanate. Another reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe, a dropping funnel and a cooling pipe was charged with 174.8 g of γ-aminopropyltrimethoxysilane, and the above obtained polyester-urethane which contains isocyanate groups at both ends was continuously added thereto, under agitation and in a nitrogen atmosphere at a temperature of 20°C over a period one hour, and reacted further at a temperature of 60°C for another 30 minutes to obtain a aminosilane-modified resin. After confirming that the infrared absorption at 2270 cm⁻¹ had disappeared, 228 g of xylene, 60 g of isopropylalcohol, and 12 g of ortho-methylacetate were added to obtain a curable resin containing N,N'-disubstituted urea groups (solids-content concentration, 60%). The viscosity of the curable resin solution was 500 cps at 23°C. In the obtained curable resin, the infrared absorption at 1640 cm⁻¹ of the urea bond was observed, and its number-average molecular weight by GPC method was 1250. Synthetic Example A reactor equipped with an agitator, a thermometer, a nitrogen-introduction pipe, a cooling pipe and a dropping funnel was charged with 200 g of butyl acetate and heated to 110°C. A solution in which 72 g of styrene, 23 g of n-butyl acrylate, 296 g of methylmethacrylate, 33 g of stearylmethacrylate, 47 g of γ-methacryloxypropyltrimethoxysilane, 29 g of acrylamide, and 9 g of azobisisobutyronitrile were dissolved in 43 g of isopropanol, was added dropwise therein, and a solution of 1 g of azobisisobutyronitrile and 80 g of butylacetate was further added dropwise for over 2 hours. The reaction of the mixture was continued at a temperature of 110°C for one hour to obtain a vinylpolymer containing silyl groups (solids-content concentration, 60%). A number-average molecular weight of the vinylpolymer containing silyl group obtained by GPC was 8000. Example 8 Comparative Examples 3 and 4 physical properties of a mixture composed of curable resin and vinyl resin containing silyl group A curable resin and a vinyl resin containing silyl group were mixed together according to a combination and a mixing ratio defined in Table 2 below, and adjusted a solid-content concentration of the mixture with butylacetate to 37%. One weight part of dibutyltin-dilaurate was added to the mixture based on 100 parts of solid content of resin to form a clear paint. Several drops of the clear paint thus obtained were dropped on a glass plate. On the other hand, a polished mild steel plate having 150 mm x 70 mm x 0.6 m of thickness was polished to a surface roughness #240, degreased and spray-coated with CAB alkyd resin to form CAB alkyd metallic base on the steel surface. After curing thereof at a room-temperature for 20 minutes, the clear paint was spray-coated thereover. A thickness of the coated films was 20 µm the CAB alkyd metallic base and 50 µm at the clear paint coating. After holding the steel plate at a room-temperature for 7 days, the films were tested and evaluated. The results are shown on Table 2 below.

Claims: A process for the preparation of room-temperature curable resins which comprises reacting a compound (A) containing at least two acryloyl groups and/or methacryloyl groups and having a number-average molecular weight from 100 to 100,000 with an amino-silane compound (B) of the general formula (wherein X is a hydrolyzable group selected from the group consisting of halogen, alkoxy, acryloxy, ketoximate, amino, acid amide, aminoxy, mercapto, alkenyloxy groups; R₁ is a C₁-C₁₀ alkyl group, aryl group, or aralkyl group; R₂ is a C₁-C₁₀ bivalent alkyl group, aryl group, or aralkyl group; n is an integer of from 1 to 3, and m is an integer of from 1 to 10), at a ratio of at least 0.2 equivalents of primary amino groups contained in the compound (B) to one equivalent of acryloyl groups and/or methacryloyl groups contained in the compound (A), under substantially water-free conditions, subsequently reacting the reaction product of the aminosilane-modified resin with a monofunctional isocyanate compound (C) represented by the general formula R₃ - NCO (wherein R₃ is a C₁-C₂₅ alkyl group, aryl group, aralkyl group, at a ratio of from 0.9 to 1.5 equivalents to one equivalent of active hydrogen of amino groups contained in the aminosilane-modified resin, and under substantially water-free conditions to obtain a room-temperature curable resin having an amine value of 2 mg KOH or lower. A process for the preparation of a room-temperature curable resin according to Claim 1 wherein the main chain of the compound (A) is principally a polyester. A process for the preparation of a room-temperature curable resin according to Claim 1, wherein the main chain of the compound (A) is principally a polyether. A process for the preparation of a room-temperature curable resin according to Claim 1 wherein the main chain of the compound (A) is principally an organopolysiloxane. A process for the preparation of a room-temperature curable resin according to Claim 1, wherein the main chain of the compound (A) contains an urethane bond. A process for the preparation of a room-temperature curable resin as claimed in Claim 1 wherein the compound (B) is γ-aminopropyltrimethoxysilane. A process for the preparation of a room-temperature curable resin as claimed in Claim 1 wherein the compound (B) is γ-aminopropyltriethoxysilane. A process for the preparation of a room-temrature curable resin as claimed in Claim 1 wherein the compound (B) is N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane. A process for the preparation of a room-temrature curable resin according to Claim 1 wherein the compound (C) is γ-isocyanatepropyltriethoxysilane. Room-temperature curable resin, obtainable according to the process of claims 1 to 9.

Inventors: FURUKAWA HISAO, KAWAMURA JO, FURUKAWA, HISAO, KAWAMURA, JO
Applicants: KANEGAFUCHI CHEMICAL IND, KANEGAFUCHI KAGAKU KOGYO KABUSHIKI KAISHA
Application year: 1987
Main classification: C08G85
IPC codes: C08F290, C08G63, C08G18, C08F22, C08F299, C08F8, C08G85, C08F20, C08G71