POLYURETHANE RESINS AND POLYURETHANE RESIN COATING COMPOSITIONS

Abstract: Polyurethane resins are provided by the reaction of polyols with trifunctional isocyanates of the following general formula wherein R is a divalent hydrocarbon group with 2 or 3 carbon atoms. The reaction between the polyol and the trifunctional isocyanate is effected at an NCO/OH mole ratio of 0.5 to 2.0 and adjustments are made so that the concentration of the carbamide groups is 5 x 10⁻⁴ to 50 x 10⁻⁴ moles per gram of the reaction product, and that the bridging parameter is 150 to 1,500. The resins may be used for polyurethane resin coatings.

Description: Polyurethane Resins and Polyurethane Resin Coating Compositions Field of the Invention The present invention relates to polyurethane resins which are beneficial as material producing a polyurethane resin coating in particular with excellent weather re distance Description of the Prior Art Polyurethane resins are classified in two types according to the kind of isocyanate compounds contained in them, i.e. the "yellowing" and "non-yellowing" types. Isocyanates which have hitherto been used for producing polyurethane resins of the non-yellowing type include for example such aliphatic isocyanates as hexamethylenediisocyanate, isophoronediisocyanate, 2,2,4-trimethylhexamethylenediisocyanate, dicyclohexylmethanediisocyanate, etc.; and xylilenediisocyanate, etc. Whilst non-yellowing type poly urethane resins obtained by causing these isocyanates to react with polyols have been employed as coating materials, many problems still remained to be solved for using them for such a purpose. One of these problems is their toxicity. Since isocyanate compounds are substances which are chemically highly reactive, they are very dangerous when used by persons who are of an allergic constitution or have weak respiratory organs. Because of this, the limit of concentration in the atmosphere of, for instance, monomers of toluenediisocyanate, diphenylmethanediisocyanate, etc., was fixed at 0.02 ppm by the Commission of the American Conference of Governmental Industrial Hygienists. For such reason, for one thing, the aforesaid isocyanate monomers are seldom used as they are in polyurethane coatings, except in special cases, but are generally used after having been modified into prepolymers, i.e. adducts obtained by adding them to trimethylolpropane, ethylene glycol, etc. This modification has the effect of lowering the vapor pressure, thereby reducing toxicity and unpleasant odor, and, in addition, of allowing the adjustment of reactivity to be made and the diversification of the type of coatings to be realized. Since, however, it is extremely difficult from an industrial point of view to wholly eliminate isocyanate monomers in the prepolymer additions, the fact still remains that one smells a strong irritating odor while engaged in the work of preparing coating materials or of applying coatings, many people complaining of the symptoms of respiratory diseases contracted by inhaling isocyanate vapor With an increase in the use of polyurethane products, this problem is of major importance. With the isocyanate additions, in particular, it is said that a dissociation to diisocyanates, which are highly toxic monomers, occurs while they are being stored, depending upon the storage conditions. For this reason, measures are being taken to improve the working environment such as for instance ensuring good ventilation, so that the operators will not directly inhale vapor of isocyanate compoundsHowever, the state of affairs in this connection is still far from being satisfactory. The second problem in conventional technology is that much remains to be desired in respect of the weather resistance of conventional coatings. Although the nonyellowing type polyurethane resins were originally developed with a view to improving the weather resistance of coatings, they are not, as yet, suffi- ciently resistant to weather under severe outdoor conditions over a long period of time, such as is necessary for automobiles, railroad carriages, aircrafts, ships, building materials, ete. The third problem concerning polyurethane coating materials is that the range in which the selection of solvent composition can be made is not wide enough, and in many cases, if the amount of solvent is reduced to save energy and prevent environmental pollution, the resultant product being a so-called "high solid type" coating with a high concentration of polyure- thane resin, the coating efficiency is much impaired because of its high viscosity. SUMMARY OF THE INVENTION The object of the present invention is to provide polyurethane resins and polyurethane resin coatings having high weather resistance and providing an improved coating efficiency. This object is solved by a polyurethane resin characterized in that it is a reaction product -obtained reacting (A) a polyol with (B) a trifunctional isocyanate of the following general formula: EMI4.1 wherein R is a divalent hydrocarbon group with 2 or 3 carbon atoms at an NCO/OH mole ratio of 0.5 to 2.0, and in which the concentration of the carbamide group is 5 x 10-4 to 50 x are moles per gram of said reaction product, and the bridging parameter 150 to 1 9,560. The polyurethane resins and coating compositions of the present invention exhibit excellent weatherresistance and improved coating characteristics. DESCRIPTION OF THE PREFERRED EMBODIMENTS A polyol as referred to in the present invention means a compund or polymer containing two or more hydroxyl groups per molecule. Examples of polyols are: diols, triols, tetraols, pentols and hexitols as well as polymer polyols such as polyesters containing two or more hydroxyl radicals per molecule (hereinafter called "polyester polyol"), polyethers containing two or more hydroxyl groups per molecule (hereinafter called "polyether polyol6'), acrylic polymers containing two or more hydroxyl radicals per molecule (hereinafter called "polyacryl polyol"), etc. These polyols may be used singly or as a mixture of two or more kinds. Further examples of preferred polyols are indicated hereinafter. Diols: ethylene glycol, propylene glycol, B;B'-dihydroxy- diethyl ether (diethylene glycol), dipropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, polyethylene glycol, polypropylene glycol, poly propylene-polyethylene glycol, polybutylene gly col; Triols: glycerine, trimethylol propane, 1,2,6-hexane triol; Tetraols: pentaerythritol, 2-methylglucoside; Hexitol: sorbitol; Polyester polyols: These are prepared by a condensation reaction between a polybasic acid, such as adipic acid, dimer acid, phtalic anhydride, isophthalic acid, etc., and a diol or triol, such as ethylene gly col, diethylene glycol, propylene glycol, trimeth ylol propane, glycerine, etc. Polyester polyols: These are prepared by adding propylene oxide ethylene oxide, or the like, to a polyhydric al cohol, such as glycerine, propylene glycol, etc. This category also includes polyether polyols rich in hydroxyl radicals obtained by causing a multi functional compound such as ethylene diamine, ethanolamine, , etc . to react with ethylene oxide or propylene oxide. Polyacryl polyols: Copolymers of an acrylic acid ester or metha crylic acid ester containing a hydroxyl group ex pressed by the following. general formula: EMI7.1 wherein n = 1, 2 or 3 R1 = hydrogen or methyl R2 = asubstituted or non-substituted hydrocarbon group with 2 to 12 carbon atoms and a monomer capable of being copolymerized therewith. Examples of acrylic acid esters or methacrylic acid esters containing hydroxyl groups are: 2-hydroxyethyl acrylate, 2-hydroxypropyl acryl ate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypentyl methacrylate, methacrylic acid monoester of glycerine, ac rylic acid or methacrylic acid monoester of trimethylol propane, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-chloropropyl methacryl ate, etc. Among these the most preferred are: 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxypropyl methacrylate. Examples of monomers which are capable of being copolymerized with the above-mentioned acrylic acid or methacrylic esters containing a hydroxyl group are given hereinafter. (1) acrylic acid or its esters, for example, acrylates of methyl, ethyl, propyl, butyl or 2-ethylhexyl (2) methacrylic acid or its esters, for example, methacrylates of methyl, ethyl, butyl, decyl, 2-ethylhexyl or lauryl (3) styrene or its derivatives, for example, -&alpha;methylstyrene, ss-chlorstyrene, etc. (4) vinyl esters5 for example, vinyl acetate, vinyl propionate, vinyl isopropionate, etc. (5) nitriles, for example, acrylonitrile,. methacrylonitrile, etc. Among these the most preferred are: methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, lauryl methacrylate, acrylic acid, methacrylic acid, styrene, acrylamide and vinyl acetate. To prepare polyacryl polyols best suited for the purpose in question, it is desirable that the amount of each monomer used be selected from the following ranges. (A) Hydroxyalkyl(meth)acrylate 5 5 to 30 % by wt. (B) Alkyl ester of acrylic acid and/or of methacrylic acid 50 to 95 % by wt. (C) Other monomer(s), as the occasion demands 0 to 50 % by wt. (D) Acrylic acid or methacrylic acid . ... 0 O to 10 % by wt. If, of the foregoing, the amount of hydroxyalkyl (meth)acrylate is less than 5 % by wt., the de gree of bridging by reaction with-isocyanate com pounds becomes too small and hence it will be impossible to obtain an excellent film coating. While the preparation of polyacryl polyols by copolymerization of monomers as described above may be carried out by any of the known polymerization methods such as solution, block, emulsion and suspension polymerization, it is preferred to polymerize in solution. A variety of polyols may be used, but, in general polyester polyols or polyacryl polyols are preferred. As for the molecular weight of polyols used a selection may be made from quite a wide range according to the purpose for which they are intended. For the "high solid type" coating, however, a range of 500 to 5,000, especially 500 to 3,000, is preferred. More particularly, when polyester polyols are used, those with a molecular weight in the range of 500 to 1,000 are best suited; whereas when polyacryl polyols are used, those with a molecular weight in the range of 1,000 to 3,000 are preferred. When preparing coatings which are not of the "high solid type" polyols with a molecular weight higher than ordinary are employed. The trifunctional isocyanate compounds employed in the present invention are those expressed by the general formula previously indicated, typical examples of which include: 2, 6-diisocyanate caproic acid -B-isocyanate ethyl ester; 2, 6-diisocyanate caproic acid -y-isocyanate propyl ester; 2, 6-diisocyanate caproic acid -2 methyl-B-isocyanate ethyl ester. All of these can be prepared by reacting an ester of lysine and aminoalcohols with phosgene. It is difficult to achieve polymerization if the carbon number of R in the aforesaid general formula is 1; whereas if the carbon number is 4 or higher, the content of isocyanate in the trifunctional isocyanates becomes too small, and this will be de trimental to the physical properties of polyurethane resin films obtained by reaction with polyols and will furthermore increase the viscosity of the trifunctional isocyanate compounds, thus making the product less suitable. By adjusting the NCO/OH mole ratio, the physical pro pestles and hence the efficiency of the product, including its film strength, flexibility, chemical resistance, solvent resistance, etc., can be modified within a wide range, thereby making it suitable for specific purposes. Compounds of which the NCO/OH mole ratio is in the range of 0.5 to 2.0 are suitable for the manufacture of films and for the application of film coatings. For polyurethane coatings in particular, the range of 0.5 to 1.2 is preferred. If the NCO/OH mole ratio is below 0.5 the hot water and acid resistance of the film coatings produced is lowered, and this results in poorer weather resistance. When the ratio is above 2.0 the resistance to weather is also affected. Those with an NCO/OH mole ratio in the range of 0.5 to 1.0 may be used advantageously for such fields as electrical insulation, capsulation, and the manufacture of cast products. When the NCO/OH mole ratio is in the range of 0.1 to 0.7, the compounds may be advantageously utilized for the manufacture of highly efficient adhesives or hardening agents. When, on the other hand, the NCO/OH mole percentage is greater, the compounds are suitable fdr the manufacture of foam products. The foaming may be achieved by introducing a certain amount of water or a blowing agent into the reaction products, by utilization of the known techniques of foaming. It is essential that the concentration of the carbamide contained in the reaction product between the polyol and the trifunctional isocyanate be in the range of 5 x 10 4 to 50 x 10 4 moles per gram of said reaction product. The term "carbamide radical8' as here- in used indicates a group expressed by: EMI13.1 which exists in the urea bond, urethane bond, biuret bond and allophanate bond. In an IR analysis, the existence of this carbamide radical can be confirmed from a peak in the vicinity of 1530 cm1. If the concentration of the carbamide radical is lower than stated, it is impossible to obtain a film coating which excels in durability, pliability, solvent and chemical resistance and adhesive power If, on the other hand, the concentration is higher than stated, the film coating will have poorer resistance to weather. It is further essential that the bridging parameter E (calculated value) of the aforesaid reaction products be in the range of 150 to 1,500. If it is below this lower limit, the pliability of a film coat obtained will be very poor. If, on the other hand, it is above the upper limit, a film coating of high durability cannot be obtained. Here, the bridging parameter Ec indicates a parameter defined by T.C. Patton (Off. Digest, 34 - 446, 348 '62) , as W1 + W2 Ec = ######### wherein W1 = weight of polyol; W2 = weight of isocyanate; F1 = degree of functioning of polyol; F2 = degree of functioning of isocyanate; C1 = degree of bridging function of polyol, C1 = F1 - 2; C2 = degree of bridging function of isocyanate, C2 = F2 - 2; E1 = equivalent weight of polyol; and E2 = equivalent weight of isocyanate. The polyurethane resins of the present invention can be used for one-component as well as for two-component type compositions. They are used as two-component type coatings most advantageously. (1) Two-Component, Polyol Hardening Type This is a two-component type polyurethane resin coating consisting of a kneaded mixture of a polyol and a pigment, the latter being added optionally ("A" liquid) and a trifunctional isocyanate, diluted with a solvent as required ("B" liquid). In use, "A" and "B" liquids are mixed together and, when necessary, the viscosity is adjusted by the use of a thinner. For mixing the two liquids a two-liquid gun may preferably be employed. It is desirable that the mixing ratio be determined in such a manner that the NCO/OH mole ratio will be 0.5 to 2.0, the concentration of the carbamide radical 5 x 10-4 to 50 x 10-4 moles per gram of the reaction product, and the bridging parameter 150 to 1,500. The solvent of the "B" liquid and the thinner of the mixture, which are used as required, may be either the same or different; but, in the latter case, it is necessary that the two are compatible with each other. Further, these must not be reactive with isocyanates and polyols, such as those containing active hydrogen atoms. Some examples of solvents that may used are given below. Hydrocarbon solvents benzene, toluene, xylene, and aromatic naphtha. Ester solvents: ethyl acetate, butyl acetate, cellosolve, hexyl acetate, amyl acetate, ethyl propionate, and butyl propionate. Ketone solvents: acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, and cyclohexanone. Glycol ester solvents: ethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether acetate. According to the present invention more than 50 % by wt. of the whole solvent composition can bye hydrocarbon solvents. Further, the amount of solvent in the "B" liquid can be as small as O to 50 % by wt., and this also constitutes a characteristic feature of the coatings of the present invention. This makes it easier to obtain a "high solid type" coating which is a factor contributing to the improvement of the outward appearance of the film coatings. As for polyols to be used, those which were previously mentioned, i.e. polyester polyols, polyether polyols, polyacryl polyols, etc., are preferred. By combining differenkkinds of polyols and isocyanate compounds, it is possible to obtain coatings of varied properties, from soft to hard and tough ones, all of which-exibit excellent resistance to weather, water, chemicals and stain. Coatings of this type are ordinarily used at temperatures ranging from room temperature to 12BQC. They display an excellent adhesive property when used for coating such materials as ferrous and nonferrous metals, plastics, rubber, leather, concrets, etc., and hence have a wide range of applications in such fields of industries as the manufacture ot building materials, automobiles, machines and instru ments, and woodworks; building of aircrafts, railroad carriages and ships, and so forth (2) One-Component, Heat Curing Type With coatings of the two-component polyol hardening type which have been described in the foregoing, the reaction progresses even at room temperature Hence cases frequently arise where the pot life of coatings in use presents a problem. In this type of coating, a one-liquid, heat curing type, the isocyanate group of the isocyanate compound is blocked by the addition of a blocking agent so that the coating will be stable at room temperature. After having been applied the coating is heated to dissociate the blocking agent. The isocyanate group is thus activated again and is caused to react with the hydroxyl group to form a film coating This method is best suited for such applications as coatings for automobiles on a manufacturing line, or the like, where it is necessary to ensure stability of coating materials while they are in store at room temperature. Polyester polyols and polyacryl polyols are preferred, as polyols to be combined with the blocked type isocyanate prepolymer. As blocking agents for the purpose of masking free isocyanate radicals of the trifunctional isocyanate compounds used in the present invention, those which are generally known may be used. Some examples of such blocking agents are: phenol, m-nitrophenol, p-chlorophenol, catechol, ethyl malonate, acetylacetone, ethyl acetoacetate, cresol, -caprolactam, methyl ethyl ketoxime, cy clohexanoneoxime, butyl mercaptan, methanol, eth anol, ethylene chlorohydrin. Although the temperature at which the above-mentioned blocking agents are dissociated varies with the kind of agent, it is generally accepted that heating to at least 1200C ist required. Since the coating of this type thus requires baking at a relatively high temperature, it has hitherto been in use mainly in such fields as the manufacture of electric wires, etc. It is expected, however, that there will be new developments in its utilization, such as adaptation to a powder paint with polyurethane resin base, to an aqueous emulsion paint, and so forth Solvents for this type of coating, which are used as the occasion demands, are identical with those in the case of the two-component type coatings. Similarly, in this case more than 50 % by wt. of the whole composition of solvents can be hydrocarbon solvents The coating compounds according to the present invention can be applied to articles to be coated in an ordinary method of coating, such as spray, brush or roller coating, or dipping. It also permits the use of commonly used picrnents and plasticizer, or other kinds of additives which are used in small amounts when Preparing a paint or when applying it in usual amounts. When choosinq Pigments as in the case of selectinq solvents, it is necessary to pay attention to their water content, as well as to their properties. It is to be noted that extenders, in particular; have a high degree of water adsorbability Catalysts may also be used to accelerate drying and hardening. For instance, such tertiary amines as dimethylethanolamine, triethylenediamine, etc., and such organic salts of tin as dibutyl tin dilaurate, etc., may be employed. The characteristics of the coatings according to this invention are as follows: (1) They have excellent gloss retention and anti cracking properties. (2) They show an excellent resistance to acid and water. It is assumed that these properties originate from the fact that the coatings harden very quickly after application and are due to the network-like structure of the coating produced by hardening with the trifunctional isocyanate compound used in the present invention. (3) The outward appearance of the coating is improved. Whilst the luster and build of a coatinq are related to various factors, the influence of the coatinq on the undercoatinq is a factor which must not be disreqarded. With the compounds of this invention, it is possible to use a variety of solvents and, in particular, aromatic solvents. This Permits the lessenina of the influence of the coating on the undercoatina. e.a. a Drimer surfacer: that means that the Dermetion of the solvent is kent at a minimum. thus helnina to achieve an imnrovement in the outward appearance of the coating. Thus, it is best suited for such purposes as the coating of automobiles, etc., where the emphasis lies on good outward appearance (4) Coatings of the "high solid type" can be formulated. Among the recent restrictions as regards environ- mental pollution, the development of polyurethane resin coatings of the "high solid type" or of the solvent less type is attracting a good deal of attention. Isocyanate as an ingredient of such coatings is required, as in the case of the polyol ingredient, to have low viscosity at room temperature. As the trifunctional isocyanate used in the present invention has a low molecular weight, it also has a low viscosity, and hence it may be used for the manufacture of coatings that will help to prevent environmental pollution. It is also possible by the proper choice of polyols to manufacture solventless coatings and thus to contribute to the saving of resources or energy. The coating of the present invention is, because of its low viscosity1 also excellent in respect of coating work efficiency. (5) The hardening speed is high. Although the hardening speed at room temperature hardly differs from that of coating materials on the market, it becomes considerably higher than the latter with the rise of the baking tempera ture. Thus, it is possible to shorten the time required for curing. (6) The degree of toxicity is low. Hexamethylenediisocyanate prepolymers or adducts have, in general, a rather strong irritating odor. This is attributed to the existence of a very small amount of hexamethylenediisocyanate monomers in the prepolymers or adducts. On the other hand, the trifunctional isocyanate compounds employed in the present invention have a remarkably low vapor pressure and there is no liberation of highly poisonous volatile ingredients while they are kept in store. Furthermore, their NCO content is higher than that of coating materials on the market. Therefore, the coatings of this invention emit little irritating odor. Besides, since the proportion.of the isocyanate ingredient to that of the polyol ingredient may, in view of its high NCO content, be reduced, this is quite advantageous from the viewpoint of hygene. Apart from its use as a coating material as described above, the polyurethane resin of the present invention may be used in various industrial fields. For instance,. those with an NCO/OH mole ratio in the range of 0.5 to 1.0 may be advantageously used for such fields as electrical insulation, capsulation, and the manufacture of-cast- products. When the NCO/OH mole ratio is in the range of 0.1 to 0.7 the compounds may be advantageously utilized for the manufacutre of highly efficient adhesive or hardening agents When, on the other hand, the NCO/OH mole ratio is greater, the compounds are suitable for the manufacture of foam products. Foaming may be achieved by introducing a certain amount of water or a blowing agent into the reaction product1 utilizing the known foaming techniques. The invention will now be further illustrated by way of examples. "Part or parts" of the compositions shown in the examples, denote "part or parts by weight". Polymerization of 2,6-diisocyanate caproic acid - Fisocyanate ethyl ester as a trifunctional isocyanate compound 122.2 g (2.0 moles) of ethanolamine, 100 ml of o-dichlorobenzene and 420 ml of toluene were put in a fourmouthed flask fitted with a stirrer, a thermometer, a gas-introducing tube and a reflux condenser combined with a Dean-Stark apparatus. By introducing hydrogen chloride gas under ice cooling ethanol amine was converted into hydrochloride. Subsequently, 182.5 g (1.0 mole) of lysine- monohydrochloride were added; by heating the mixture to a reaction temperature of 80 Ca hydrochloride of ethanolamine was caused to melt; and then by introducing into it hydrogen chloride gas, it was converted into lysine -dihydrochloride. The passing of hydrogen chloride gas through the compound at a rate of 20 to 30 ml per min., with the reaction mixture heated to the reflux temperature (1160C) was continued and this temperature was maintained until there no longer was any distillation of water. The reaction was allowed to continue for approximately 8 hours; thereafter, the solvent was decanted, and a mixture of methanol and ethanol was added to the resultant oillike substance and heat was applied.When this product was left standing at room temperature, a deposition of crystals occured. By filtering out these crystals, 165 g of tertiary hydrochloride of lysine-B-aminoethyl ester having a melting point of 175"C, recrystallized from a mixture of methanol and ethanol, was obtained. This trihydrochloride was pulverized and was then vacuum-desiccated at 500C for 8 hours. Subsequently, it was put in a four-mouthed flask provided with a stirrer, a thermometer, a gas-introducing tube and a reflux condenser, and a suspension was obtained by pouring 2.1 lit. of o-dichlorobenzene into it. While stirring this suspension, phosgen was passed through it at a rate of 2.8 moles/hr., and the suspension was heated at 1200C for 10 hours. When the temperature was gradually raised to 1500C over a period of 6 hours, the suspensoid was practically wholly dissolved in the liquid. After cooling, the liquid was filtered and the solvent was elimiated by distillation under reduced pressure. The residue was distilled under nitrogen gas flow using an oil diffusion pump. The product, 140 g (yield 90%) of lysine isocyanate-B-isocyanate ethyl ester (2, 6-diisocyanate caproic acid -ss-iso- cyanate ethyl ester) (hereinafter referred to as "LTI- E" was a colorless, transparent liquid with a boiling point of 155 to 1570C/0.022mmHg. Viscosity: 29 cps/20 C. NC0 content 47.1% by wt. (calculated value 47.2% by wt.). Infrared spectrum 2225 (isocyanate group), 1745 cm (ester carbonyl), 1460, 1355, 1200cm-1 (ester ether) Nuclear magnetic resonance spectrum: 1.2 to 2.3 ppm (6H), 3.2 to 3.95 ppm (4H, - CH2 - NCO), 4.0 to 4.7 ppm EMI25.1 Mass spectrum m/c 153 (OCNCH2CH2CH2CH2 - CHHCO), 267 (molecular weight). Polymerization of 2, 6-diisocyanate caproic acid &gamma;-isocyanate propyl ester as a trifunctional iso cyanate compound 30 g (004 mole) of 3-aminopropanol and 100 ml of toluene were introduced into a four-mouthed flask fitted with a stirrer, a thermometer, a gas introducing tube and a reflux condenser combined with a Dean-Stark apparatus: By introducing hydrogen chloride gas, 3-aminopropanol was converted into the hydrochloride Then, 36.6 9 (002 mole) of lysine monohydrochloride were added, and by again introducing hydrogen chloride gas into the mixture it was converted into dihydrochloride of lysine. The reacting mixture was heated to the reflux temperature (1100C) and, meanwhile, hydrogen chloride gas was passed through it. After 11 hours the azeotropic distillation of water ceased. Toluene was eliminated from the resultant product, and ethanol was added to the residual oil-like substance and heat was applied to the mixture. When this product was allowed to stand at room temperature, a deposition of crystals occurred. By filtering these crystals, 47 g of trihydrochloride monohydrate of lysine-y-aminopropyl ester having a melting point of 138 to 1450C, recrystallized from a mixture and ethanol, was obtained. Then 25 g of desiccated powder of trihydrochloride monohydrate of lysine-Y-aminipropyl ester, polymerized as above, and 300 ml of o-dichlorobenzene were put in a four-mouthed flask provided with a stirrer, a thermometer, a gas-introducing tube and a reflux condenser so as to form a suspension. While maintaining the temperature of the suspension at 1050C, phosgen was passed through it at a rate of 0.4 mole/hr. for TO hours. Then the temperature was gradually raised to 15O0C, and the reaction was allowed to progress at this temperature for 4 hours. After cooling, the liquid was filtered and the solvent was eliminated by distillation under reduced pressure. The residue was made to undergo a molecular distillation. The product was 7.2 g (yield 34%) of lysine diisocyanate -Y-isocyanate propyl ester (2, 6-diisocyanate caproic acid -Y-isocyanate 'propyl ester) (hereinafter referred to as "LTI-P" a light yellow liquid with a boiling point of 153 to 1550/0.036mmHg. Viscosity: 28 cps/20 C. NCO content: 44.6% by wt. (calculated value 44.8% by wtO -1 Infrared spectrum: 2225 cm (isocyanate group), 1740cm (ester carbonyl), 1458, 1350, 1200cm-1 (ester ether). Nuclear magnetic resonance spectrum: 1.2 to 2.4 ppm (8H), 3.2 to 3.8 ppm (4HF -CH2 NCO), 3.9 to 4.6 ppm EMI27.1 Mass spectrum; m/c 153 (OCNCH2CH2CH2CH2CHNCO), 281 (molecular weight). Example 1 In a reactor provided with a stirrer, a thermometer, a condenser and a nitrogen gas introducing tube after purging with nitrogen gas, 50 parts xylole and 50 parts butyl acetate were introduced, and the temperature was raised to a value between 90 and 95 C. A mixture composed of: styrene 34.0 pts. n-butyl acrylate 38.0 pts. 2-hydroxyethyl methacrylate 23.4 pts. acrylic acid 0.4 pt. and azobisisobutylonitrile 1.2 pts. was continuously dropped into the reactor over a period of 3 hours, to effect the polymerizing reaction. After having finished dropping the mixture of monomers, the compound was stirred for 1 hour while it was heated Thereafter, 0.7 part of azobisisobutylonitrile were added 4 times at an interval of 30 minutes, and the compound was stirred for another hour to complete the reaction. The resin solution thus obtained (a solution of polyacryl polyol) was colorless and transparent. Its Gardener bubble viscosity was "T" to "V" at 250C, and the content of nonvolatile matter 50%. The molecular weight (Mn) was 14500; value of hydroxyl group 50; and calculated value of mean number of hydroxyl groups in a molecule 25.8. This resin solution and LTi-E, which had been previously prepared, were uniformly blended in such a manner that the amounts of hydroxyl and isocyanate groups were equal. A mixed thinner composed of toluene and cellosolve acetate, in the ratio of 65/35% by wt., was added to this blended solution to adjust the fluidity to 20 sec. at +4 of the Ford cup. This diluted coating material was applied by spraying it on a mild steel sheet, previously coated with primer surfacer (No. llAmfrd. by Kansai Paint Co.) and polished, in such a manner that the film thickness after drying was approximately 40ss, and the coating was allowed to harden at room temperature (230C) for a week. The film coating obtained was, as is shown in Table 1, hard and had an excellent resistance to acid and hot water. In respect of anti-yellowing property, too, it was equal to a coating obtained by the use of non- yellowing type isocyanate prepolymers on the market. The concentration of the carbamide group was 1507 x 10 4 moles/g; the bridging parameter was 501, and the percentage of hydrocarbon solvent in the solvents contained in the coating material was 59. Example 2 A coating was formed in the same manner as Example 1, except for the fact that the mixing ration of polyacryl polyol solution and LTI-E was modified so as to obtain an NCO/OH mole ratio of 0.5. The properties and efficiency of the coating obtained are shown in Table 1. The concentration of the carbamide groups was 8.4 x 10-4 moles/g; the bridging parameter was 947; and the percentage of hydrocarbon solvent in the solvents contained in the coating material was 59. Example 3 A coating was formed in the same manner as Example 1, with the exception that the mixing ratio of polyacryl polyol solution and LTI-E was modified so as to obtain an NC0/OH mole ratio of 1.5 The properties and efficiency of the coating obtained are shown in Table 1. The concentration of the carbamide group was 22.0 x 10 mole/g.; the bridging parameter was 558; and the per- centage of hydrocarbon solvent in the solvents contained in the coating material was 58. Example 4 In the reaction apparatus as was used in Example 1, after purging it with nitrogen gas,80 parts xylole and 20 parts butyl acetate were introduced and the temperature was raised to between 80 and 850C. A monomer mixture composed of: styrene 25.0 pts. methyl methacrylate 25.0 pts. n-butyl methacrylate 21.0 pts. n-butyl acrylate 14.0 pts. 2-hydroxyethyl methacrylate 12.0 pts. acrylic acid 0.7 pts. and azobisisobutylonitrile 1.2 pts. was continuously dropped into the reactor over a period of 3 hours. With the dropping ceased, the reaction mixture was heated and stirred for 2 hours. Subsequently, 0.5 parts of azobisisobutylonitrile were added 4 times at an interval of 2 hours, and the mixture was further heated and stirred for 3 hours to complete the polymerization reaction. The resin solution thud obtained was colorless and transparent. Its Gardener bubble viscosity (250C.) was "V" to "W", and the content of non-volatile matter was 50%. The molecular weight (Mn) was 11700;- the value of the hydroxyl groups was 25 and the calculated value of the average number of hydroxyl groups in a molecule 10.4. A coating material was prepared with this resin solution applied and was allowed to harden in the same manner as in example 1. As shown in Table 1, a coating having a good luster, with satisfactory rise of hardness and excellent resistance to acid and hot water was obtained. Also in respect of the anti-yellowing property the coating was as good as one obtained by the use of nonoyellowing type isocyanate prepolymers available on the market, i.e. no yellowing was observed. The concentration of carbamide groups was 8.4 x 10 moles/g.; the bridging parameter was 1,0672 and the percentage of hydrocarbon solvent in the solvents contained in the coating material was 71. Example 5 LTI-P, which had been previously prepared by polymerization was added to the resin solution obtained in Example 4 in such a manner that the amounts of hydroxyl and isocyanate groups were equal, and these were uniformly mixed to- getter A coating material was prepared with this mixture, applied and allowed to harden in the same manner as in Example 1. The properties and efficiency of the coating obtained are shown in Table 1. The concentration of the carbamide groups was 8.5 x 10 4 moles/g.-, and the bridging parameter was 1031. Comparative Example 1 A coating was formed in the same manner as Example 1, except for the fact that the mixing ratio of polyacryl polyol solution and LTI-E was modified so as to obtain an NCO/OH mole ratio of 2.50. The characteristics of the coating obtained are shown in Table 1. The concentration of carbamide groups was 32.4 x 10 moles/g.;and the bridging parameter was 633. Comparative Example 2 A coating was formed in the same manner as Example 4, except for the fact that the mixing ratio of the resin solution and LTI-E was modified so as to obtain an NCO/ OH mole ratio of 0.5. The properties of the coating obtained are shown in Table 1. The concentration of carbamide groups was 4.4 x 10 moles/g.; and the bridging parameter was 1,999. Comparative Example 3 A coating was formed in the same manner as in Example 5 except for the fact that the mixing ratio of the resin solution and LTI-P was modified so as to obtain an NCO/OH mole ratio of 0.5 5 , The properties of the coating obtained are shown in Table 1 The concentration of the carbamide groups was 4.4 x moles/g.; and the bridging parameter 1,966. Table 1 EMI34.1 Examples <SEP> and <SEP> Comparative <SEP> Ex. <SEP> 1 <SEP> Ex. <SEP> 2 <SEP> Ex. <SEP> 3 <SEP> Ex. <SEP> 4 <SEP> Ex. <SEP> 5 <SEP> Comp. <SEP> Ex. <SEP> 1 <SEP> Comp. <SEP> Ex. <SEP> 2 <SEP> Comp. <SEP> Ex. <SEP> 2 <tb> Examples <tb> Isocyanate <SEP> Compounds <SEP> LTI-E <SEP> LTI-E <SEP> LTI-E <SEP> LTI-E <SEP> LTI-P <SEP> LTI-E <SEP> LTI-E <SEP> LTI-P <tb> Items <SEP> for <SEP> Assessment <tb> Weather <SEP> Wethaometer <SEP> I <SEP> II-I <SEP> II <SEP> II <SEP> II <SEP> IV <SEP> IV <SEP> IV <tb> resis- <SEP> 2500 <SEP> hrs. <tb> tance <SEP> Exposure <SEP> out- <SEP> I <SEP> II-I <SEP> II <SEP> II <SEP> II <SEP> III-IV <SEP> V <SEP> V <tb> <SEP> doors <SEP> 2 <SEP> years <tb> Rise <SEP> of <SEP> hardness <SEP> I-II <SEP> 0 <SEP> 0 <SEP> I <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> Gloss <SEP> value, <SEP> 60 <SEP> 90 <SEP> 0 <SEP> 0 <SEP> 95 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> Lead <SEP> pencil <SEP> hardness <SEP> 3H <SEP> 0 <SEP> 0 <SEP> 2H <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> Shock <SEP> resistance, <SEP> 1 <SEP> kg <SEP> 35 <SEP> cm <SEP> 0 <SEP> 0 <SEP> 20 <SEP> cm <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> Erichsen <SEP> test <SEP> 6.0 <SEP> 0 <SEP> 0 <SEP> 7.5 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> Cross-cut <SEP> adhesion <SEP> 100/100 <SEP> 0 <SEP> 0 <SEP> 100/ <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> property <SEP> 100 <tb> Hot <SEP> water <SEP> resistance, <SEP> II <SEP> 0 <SEP> 0 <SEP> II <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> 50 Cx24 <SEP> hrs. <tb> Acid <SEP> resistance <tb> 40 <SEP> vol. <SEP> %H2SO4 <SEP> II-III <SEP> 0 <SEP> 0 <SEP> II <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> 55 Cx5 <SEP> hrs. <tb> EMI35.1 Examples <SEP> and <SEP> Comp. <SEP> Examples <SEP> Ex. <SEP> 1 <SEP> Ex. <SEP> 2 <SEP> Ex. <SEP> 3 <SEP> Ex. <SEP> 4 <SEP> Ex. <SEP> 5 <SEP> Comp. <SEP> Ex. <SEP> 1 <SEP> Comp. <SEP> Ex. <SEP> 2 <SEP> Comp. <SEP> Ex. <SEP> 3 <tb> <SEP> Naphtha <SEP> No. <SEP> 5/toluole <tb> Solvent <SEP> (6) <SEP> (4) <SEP> I <SEP> 0 <SEP> 0 <SEP> II <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> resis- <SEP> dipped <SEP> for <SEP> 10 <SEP> min. <tb> tance <SEP> "Xyloler" <SEP> rubbing, <SEP> II <SEP> 0 <SEP> 0 <SEP> II-III <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> 30 <SEP> times <tb> Yellowness <tb> Yellowing <SEP> 0 <SEP> hr <SEP> 1.3 <SEP> 0 <SEP> 0 <SEP> 3.1 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> deg. <SEP> 200 <SEP> hrs <SEP> 9.1 <SEP> 0 <SEP> 0 <SEP> 12.2 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> Color <SEP> differ- <SEP> UV* <SEP> 200 <SEP> hrs <SEP> 7.8 <SEP> 0 <SEP> 0 <SEP> 9.0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> ence <SEP> 200 <SEP> hrs <SEP> 4.7 <SEP> 0 <SEP> 0 <SEP> 5.5 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> #E <SEP> (Lob) <tb> *"Thosiba" Sterilizing Lamg GL-15 (15W), wave length Pigment Mixed: PWC 50% 254 nm; strenght of radiation at a distance of Hardening: A week, at room temperature 20 cm = 600 w/cm . (23 C). Legend: I = Very good; II = Good; III = Somewhat poor; IV = Poor; V = Very Poor; 0 = Not measured. Example 6 A polyester polyol was prepared in the following manner. A mixture composed of: neopentyl glycol 150.0 pts. trimethylol propane 22.1 pts. adipic acid 72.3 pts. and isophthalic acid 123.2 pts. was introduced into a reactor and stirred for 30 minutes while heating it at 2000C. Then, heating and stirring were continued at a temperature of 2200C until it reached an acid value of 10 and a CH value of 150, thus distilling water (approx. 15 hrs.). The molecular weight of the reaction product obtained was approximately 1000. By adding butyl acetate to this reaction product while it was being cooled, a solution with 70% solid matter content, i.e. a polyester polyol solution was prepared. Then LTI-E was added to this polyester polyol solution in such a manner that the amounts of hydroxyl and isocyanate groups were equal, and these were uniformly mixed. The calculated value of the concentration of the carbamide groups of this reaction product was 21.8 x 10 4 and the calculated value of the bridging parameter was Ec 790. A film coating which was obtained by applying this coating mixture and letting it harden had an excellent luster and very good mechanical properties. The percentage of hydrocarbon solvent in the solvents contained in said coating material was 48. Example 7 A two-component type polyurethane coating consisting of "A" and "B" liquids, as mentioned below, was prepared. "A" liquid: 171.6 parts polyacryl polyol of Example 1 and 57.2 parts titanium oxide were kneaded in a three-roller kneading machine to form a paste. "B" liquid 7.8 parts xylole were added to 142 parts LTI-E to form a triisocyanate solution with an a content of 30 wt.%. By mixing equal amounts of A and "B" liquids, a mixture of NCO/OH - 1 was obtained. By adding a thinner (toluoleXcellosolve acetate = 65/35 wt.%) to this mix ture, the fluidity was adjusted to 15 sec. of the Ford cup No. 4. The content of nonsvolatile matter in the solution was 55%. This diluted solution was applied by spraying it on a mild steel sheet previously coated with a primer surfacer and polished, such as was used in Example 1, in such a manner that the film thickness after drying was approximately 40, and the material was heated at 600C for 30 minutes. The coating obtained had'a good luster and was also superior in respect of acid and solvent- restistance. The gloss retention after exposure outdoors for 18 months was approximately 70%, thus proving to have very good weather resistance. Concentration of the carbamide group: 15.7 x 10 moles/g. Bridging parameter: 501. Percentage of hydrocarbon in the solvents: 57.1%. Example 8 Methyl ethyl ketoxime in an amount equal to that of NCO group was added to 14.2 parts LTI-E of the "B" liquid of Example 7, and the mixture was stirred for 5 hours at room temperature to block the NCO groups of LTI-E.By adding 7.8 parts xylole to this blocked isocyanate, 8 triisocyanate solution with an NCO content of 30 wt.% at the time of dissociation was prepared. By mixing this solution with the "A" liquid of Example 7, a one-liquid type polyurethane coating was prepared. The coating material was diluted with a thinner, and was applied on the base material in the same manner as in Example 7. After the coating had set, the material was heated at 1500C for 30 minutes to form a finished coating. The polyurethane resin coating obtained had a superior luster and showed satisfactory resistance to weather.

Claims: CLAIMS 1. A polyurethane resin characterized in that it is a reaction product obtained- by reacting (A) a polyol with (B) a trifunctional isocyanate of the following general formula EMI40.1 (wherein R is a divalent hydrocarbon group with 2 or 3 carbon atoms) at an NCO/OH mole ratio of 0.5 to 2.0; and in which the concentration of the carbamid group is 5 x 10 4 to 50 x 10 4 moles per gram of said-reaction product and the bridging parameter is 150.to 1,500. 2. A polyurethane resin as claimed in Claim 1, characterized in that the molecular weight of the polyol is in the range-of 500 to 5,000. 3. A film coating characterized in that it comprises as main component a polyurethane resin which is a reaction product obtained by reacting (A) a polyol with (B) a trifunctional isocyanate of the following formula EMI41.1 (wherein R is a divalent hydrocarbon group with 2 or 3 carbon atoms)at an NCO/OH mole ratio of 0.5 to 2.0; and in which the concentration of the carbamide group is 5 x 10 4 to 50 x 10 4 moles per gram of said reaction product and the bridging parameter is 150 to 1,500 4. A film coating as claimed in Claim 3, characterized in that the molecular weight of the polyol is in the range of 500 to 5,000. 5 A film coating as claimed in Claim 3, characterized in that the polyol is a polyester polyol whose molecular weight is in the range of 500 to 1,000 6. A film coating as claimed in Claim 3, characterized in that the polyol used is a polyacryl polyol whose molecular weight is in the range of 1,000 to 3,000. 7 A film coating as claimed in any of Claims 3 to 6, characterized in that the NCO/OH mole ratio is in the range of 0.5 to 1.2 8. A film coating as claimed in Claim 6, characterized in that the polyacryl polyol is a copolymer consisting mainly of hydroxyalkyl acrylate and/or hydroxyalkyl methacrylate, and alkyl ester of acrylic acid and/oralkyl ester of methacrylic acid. 9. A two-component type polyurethane resin coating characterized in that it comprises (A) a mixture of a polyol and optionally a pigment and (B) a trifunctional isocyanate. of the following general formula EMI42.1 (wherein R is a divalent hydrocarbon group -with 2 or 3 carbon atoms)and optionally comprises a solvent amounting to from 1 to 50% by weight based on the component (B).10. A coating as claimed in Claim 9, characterized in that 50% by wt. of the solvent used and the thinner optionally added is a hydrocarbon solvent. 11. A-one-component type polyurethane-resin coating characterized in that it comprises a polyole and a trifunctional isocyanate of the following general formula: EMI43.1 (wherein R is a divalent hydrocarbon group with 2 or 3 carbon atoms) and in which the isocyanate group is blocked with a blocking agent. 12. A coating as claimed in Claim 11, characterized in that more than 50% by wt. of the solvent which is optionally added is a hydrocarbon solvent

Inventors: MASAMI, SAITO, SADAYUKI, SAKAMOTO, TADANORI, FUKUDA
Applicants: TORAY INDUSTRIES, INC.
Application year: 1979
Main classification: C08G18
IPC codes: C08G18