Carbodiimide having double bonds

Abstract: A carbodiimide having double bonds represented by the formula (1): R 1 -X-(R 2 -NCN) n -R 2 -X-R 3 wherein R 1 and R 3 may be the same as or different from each other and each represents the organic residue having 3 to 40 carbon atoms, of a compound having at least one olefinic double bond and a functional group capable of reacting with an isocyanate group, formed by removing the functional group therefrom; R 2 represents the organic residue of a diisocyanate formed by removing the isocyanate group therefrom; plural R 2 groups may be different from one another; X represents a bond formed by reaction between the above isocyanate group and the above functional group capable of reacting with isocyanate group; and n represents an integer of 1 to 20. Said carbodiimide being useful as a hydrolysis stabilizer for an ester bond-containing resin or as a cross-linking agent for a compound having an olefinic double bond(s) or for a resin having a group capable of reacting with carbodiimide group.

Description: The present invention relates to a novel carbodiimide having olefinic double bonds, and more particularly, the present invention relates to a novel carbodiimide which exhibits excellent performance as a hydrolysis stabilizer for an ester bond-containing resin or as a cross-linking agent for a resin having a group capable of reacting with carbodiimide group or for a compound having an olefinic double bond. Description of Related Art Carbodiimides having a structure represented by the formula -N=C=N- have been widely used as a hydrolysis stabilizer for ester group-containing compounds or as a cross-linking agent for resins having a carboxyl group which is a group capable of reacting with carbodiimide group, for example, a cross-linking agent for acrylic resins, based on the high reactivity of the carbodiimide group. However, carbodiimides which have heretofore been employed in the above-mentioned applications are merely added to resins, and hence, are disadvantageous in that they bleed out of the resins and the desired performance is not obtained in some cases. In addition, the carbodiimide that bled out contaminates a material or the like adjacent to the resin. Moreover, when the amount of the carbodiimide added is increased for obtaining the desired performance, there is such a problem that the carbodiimide comes to function as a plasticizer and the original performance of the resin is thereby deteriorated. In particular, when the carbodiimide is used as a cross-linking agent for a hydrophilic resin having hydrophilic groups such as an acrylic resin and urethane resin, the carbodiimide must be hydrophilic as well, and hence, when the cross-linking effect is low, the carbodiimide dissolves together with the hydrophilic resin in water, whereby the water resistance and washing resistance of the resin are deteriorated. Furthermore, in order to enhance the cross-linking effect, an effort has been made to branch the carbodiimide resin or reduce the carbodiimide equivalent (the weight [g] of a carbodiimide compound necessary for giving one mole of carbodiimide group). However, when the branching is too much, the steric hindrance of the carbodiimide becomes too great and the reactivity of the carbodiimide is lowered, so that there is a limit in the branching. Moreover, the inexpensive starting material (isocyanate) for obtaining the carbodiimide is limited in kind, and hence, there is a limit to the effort to reduce the carbodiimide equivalent. The above-mentioned prior art is disclosed in JP 06192206 A and JP 63264128 A. WO 9322282 A discloses polymers containing units derived from the alphamethylstyryl group containing carbodiimide to be useful as polymeric dehydrating agents or can be used to cross-link other polymers. Further, polycarbodiimides are described to be useful in coatings. SUMMARY OF THE INVENTION The main object of the present invention is to overcome the above-mentioned difficulties of prior art and provide a novel carbodiimide having at least two olefinic double bonds which is polymerized with, when added to, an ester group-containing resin, for example, a urethane resin, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) or an unsaturated polyester; or a resin having a group capable of reacting with carbodiimide, for example, an acrylic resin, or natural rubber or synthetic rubber supplied in a form of emulsion (latex), to cross-link the resin reticularly without deteriorating the performance of the resin or without bleeding out of the resin, and hence, can be advantageously employed as a hydrolysis stabilizer or cross-linking agent for the resin. Other objects and advantages of the present invention will become apparent from the following description. According to the present invention, there is provided a carbodiimide having double bonds represented by the formula (1): R 1 -X-(R 2 -NCN) n -R 2 -X-R 3 wherein R 1 and R 3 may be the same as or different from each other and each represents the organic residue having 3 to 40 carbon atoms, of a compound having at least one olefinic double bond and a functional group capable of reacting with an isocyanate group, formed by removing the functional group therefrom; R 2 represents the organic residue of a diisocyanate formed by removing the isocyanate group therefrom; plural R 2 groups may be different from one another; X represents a bond formed by reaction between the above isocyanate group and the above functional group capable of reacting with isocyanate group; and n represents an integer of 1 to 20. According to the present invention, there is further provided a hydrolysis stabilizer for an ester bond-containing resin, which comprises as a main component a carbodiimide having double bonds represented by the above formula (1). According to the present invention, there is still further provided a cross-linking agent for a resin having a group capable of reacting with carbodiimide group or for a compound having an olefinic double bond(s), which comprises as a main component a carbodiimide having double bonds represented by the above formula (1). DETAILED DESCRIPTION OF THE INVENTION The carbodiimide having double bonds of the present invention is represented by the above formula (1), and in the formula (1), R 1 and R 3 each represents the organic residue having 3 to 40 carbon atoms of a compound having at least one olefinic double bond and a functional group capable of reacting with isocyanate group formed by removing the functional group from the compound. Incidentally, R 1 and R 3 may be the same as or different from each other As the compound having at least one olefinic double bond and a functional group capable of reacting with isocyanate group from which R 1 and R 3 , which are the above organic residues, are derived (said compound is referred to hereinafter as "double bond compound" in some cases), there can be mentioned specifically 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, glycidyl acrylate, glycidyl methacrylate, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, allylamine, N-methylallylamine, N-ethyl-2-methylallylamine, diallylamine, allylcyclohexylamine, butadiene monoxide, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, allyl glycidyl ether, 2-allylphenol, 2-allyloxyethanol, pentaerythritol triallyl ether, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monoacrylate, 2-sulfoethyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, polypropylene glycol monoacrylate and the like. Accordingly, R 1 and R 3 are the organic residues formed by removing the functional group capable of reacting with isocyanate group from these double bond compounds. In the above formula (1), R 2 represents the organic residue of a diisocyanate formed by removing the isocyanate group therefrom, and specifically represents the organic residue formed by removing the isocyanate group from an aliphatic diisocyanate such as 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate or the like, or from an aromatic diisocyanate such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, triisopropylidenephenyl diisocyanate or the like. Incidentally, R 2 may be the residue resulting from one kind of diisocyanate or from a mixture of different kinds of diisocyanates, for example, a mixture of 4,4 '-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate and isophorone diisocyanate, or the like. In the above formula (1), X represents a bond formed by reaction between the above-mentioned isocyanate group and the above-mentioned functional group capable of reacting with isocyanate group, and specifically represents a urethane bond, a urea bond, an imide bond or an amide bond, and n represents an integer of 1 to 20. In the production of the present carbodiimide having double bonds and having such a structure as mentioned above, first of all, a carbodiimide-modified diisocyanate represented by the formula (2): OCN-(R 2 -NCN) n -R 2 -NCO (wherein R 2 and n are as defined above) is produced by heating a corresponding diisocyanate in the presence of a carbodiimidization catalyst. As the above-mentioned carbodiimidization catalyst, suitable is an organic phosphorus compound, and phosphorene oxides are particularly preferable in respect of activity. Specifically, there can be mentioned 3-methyl-1-phenyl-2-phosphorene-1-oxide, 3-methyl-1-ethyl-2-phosphorene-1-oxide, 1,3-dimethyl-2-phosphorene-1-oxide, 1-phenyl-2-phosphorene-1-oxide, 1-ethyl-2-phosphorene-1-oxide, 1-methyl-2-phosphorene-1-oxide and double bond isomers thereof. Among them, 3-methyl-1-phenyl-2-phosphorene-1-oxide is particularly preferable because it is easy to obtain commercially. The above-mentioned carbodiimidization reaction can be carried out in a known manner. For example, it is sufficient to heat and stir any aliphatic diisocyanate at a reaction temperature within the range of from 150°C to 200°C in a solvent inert thereto or in the absence of any solvent, in a stream of an inert gas such as nitrogen or the like or while bubbling the inert gas, in the presence of the above-mentioned catalyst added in a proportion of 0.1 to 10% by weight (a larger amount is possible when the economy is neglected), preferably 0.5 to 5% by weight, based on the total weight of the isocyanates, to allow carbodiimidization accompanied by decarboxylation to proceed. When an aromatic diisocyanate is used, it is sufficient to heat the same and stir the aromatic diisocyanate at a reaction temperature within the range of from 20°C to 80°C in the presence of the above catalyst added in an amount of 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, in the same manner as above. In the above carbodiimidization reaction, the degree of polymerization of the carbodiimide obtained can be controlled by tracing the degree of polymerization of the carbodiimide under reaction at any time by measuring the amount of the remaining isocyanate by a titration method and cooling the reaction system to, for example, 30°C in the stage that a carbodiimide having the desired degree of polymerization has been produced, to terminate the reaction, thereby obtaining a carbodiimide having the degree of polymerization in said stage. When the desired degree of polymerization is reached, an endblocking agent (an unsaturated organic compound having a functional group reactive with isocyanate) may be introduced into the reaction system. Subsequently, the carbodiimide-modified diisocyanate obtained is reacted with the above-mentioned double bond compound in an amount equivalent to the diisocyanate by heating the two compounds in solution of a solvent inert thereto or in the absence of any solvent, to obtain the present carbodiimide having double bonds. Incidentally, in this case, a urethanization catalyst or a urethane-urea catalyst may be added to the reaction system. The solvent which can be used in the reaction between the carbodiimide-modified diisocyanate and the double bond compound may be any solvent as far as it is inert to the isocyanate, the carbodiimide and the functional group of an unsaturated organic compound and can dissolve the carbodiimide and the unsaturated organic compound. Though the solvent is not critical, preferable solvents are, for example, aromatic hydrocarbons such as toluene, benzene, xylene and the like; halogenated hydrocarbons such as chloroform, dichloroethane, Perclene and the like; and ethers such as THF and the like, and when tetramethylxylylene diisocyanate is used, ketones such as acetone and the like; amides such as DMF and the like; etc. can be used as the solvent. Incidentally, as the above-mentioned urethanization catalyst and urethane-urea catalyst, there may be used those which are generally used and the catalysts are not critical. For example, amine type catalysts are preferable because they have a high activity. The completion of the above reaction can be confirmed by the disappearance of isocyanate group which is observed at 2200-2300 cm -1 in an infrared absorption spectrum (IR). The reaction temperature and reaction time can be appropriately varied depending upon, for example, the reactivity of the carbodiimide-modified diisocyanate with the double bond compound, the kind and amount of the catalyst used, and the boiling point of the double bond compound; however, the reaction temperature is preferably 0°C to 180°C, more preferably 20°C to 160°C. When the reaction temperature is too high or the reaction time is too long, the production becomes commercially disadvantageous, and it follows in some cases that the olefinic double bonds polymerize. Therefore, such conditions are not desirable. Moreover, during the synthesis and storage, it is a matter of course to intercept a light for avoiding the polymerization, and in some cases, an adequate polymerization inhibitor may be added. However, the presence of oxygen inhibits the polymerization, so that the polymerization inhibitor is not always necessary in the presence of oxygen. That the present carbodiimide having double bonds is represented by the above formula (1) can be confirmed by an analysis of IR, a nuclear magnetic resonance spectrum (NMR), a gel-permeation chromatography (GPC) or the like. As already explained above, that the isocyanate and the functional group of the unsaturated compound have been reacted quantitatively can be confirmed based on the disappearance of absorption of isocyanate confirmed by the IR analysis. Moreover, the presence of carbodiimide group can be confirmed by the absorption at 2100-2200 cm -1 , and absorption of the bond formed by the reaction between the double bond compound and the isocyanate group of the carbodiimide can be confirmed, and, for example, in the case of the reaction between the epoxy group, alcohol group or amino group of the double bond compound and the isocyanate group, absorption of the bond formed by the reaction can be confirmed at 1700-1800 cm -1 , 1700-1800 cm -1 or 1400-1700 cm -1 , respectively. In the NMR analysis of proton, the protons of H 2 C=CH- and H 2 C=C(R)- are observed at 4.5-7 ppm and, by comparing the integration value thereof with the integration value of other protons of methyl, methylene and the like, there can be confirmed the presence of double bond in the theoretical amount. Furthermore, a styrene-reduced molecular weight is obtained by the GPC analysis and a substantially theoretical degree of polymerization can be confirmed therefrom. The present novel carbodiimide can be polymerized alone or in combination with other compounds having olefinic double bonds, namely polymerizable unsaturated monomers or oligomers or unsaturated resins, with a light, heat or a polymerization initiator if necessary, to produce a resin of higher strength. By the polymerization, there can also be obtained a novel polymer high in hydrolysis stability, heat resistance, water resistance, chemical resistance and adhesiveness to various substrates; in other words, conventional resins having said properties can be modified by the present carbodiimide. Incidentally, among the above-mentioned compounds having olefinic double bonds, the polymerizable unsaturated monomers or oligomers include such monomers as ethylene, propylene, styrene, isoprene, butadiene, acrylonitrile, vinyl chloride, vinylidene chloride, methacrylic acid, methylmethacrylic acid, acrylic acid, vinyl acetate and the like and oligomers thereof, and the above unsaturated resins include unsaturated polyester resins. When the carbodiimide of the present invention is polymerized with, for example, an unsaturated polyester resin, the strength and hydrolysis resistance of the unsaturated polyester resin can be enhanced. When the present carbodiimide is added to a resin having a group capable of reacting with carbodiimide group and they are subjected to polymerization, the water resistance and chemical resistance of the resin can be enhanced. Moreover, when the above compound having, in the molecule, at least one polymerizable unsaturated bond and at least one group capable of reacting with isocyanate group has a hydrophilic group (for example, ethylene oxide, propylene oxide, amine, quaternary ammonium salt, sulfonic acid or the like) in the molecule, a hydrophilic unsaturated carbodiimide can be obtained by controlling the degree of polymerization of the carbodiimide so as to fall within an appropriate range, and this hydrophilic unsaturated carbodiimide is useful as a cross-linking agent for hydrophilic resins. DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples are shown below to explain the present invention in more detail. Synthesis of carbodiimide-modified diisocyanates In a 5-liter reactor were placed 3.0 kg of 4,4'-dicyclohexylmethane diisocyanate (HMDI) and 15 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phosphorene-1-oxide, the same applying to the synthesis examples appearing hereinafter), and they were subjected to reaction at 185°C for 10 hours while being stirred at 200 rpm by means of a mechanical stirrer, to obtain a carbodiimide having a degree of polymerization (n) of 3.2 and having terminal isocyanate groups (referred to hereinafter as Synthesis No. A). The same procedure as above was repeated, except that the amounts of the diisocyanate and the catalyst and the reaction time were changed as shown in Table 1, to obtain carbodiimides (referred to hereinafter as Synthesis Nos. B to L). Synthesis No. Isocyanate Amount (kg) Catalyst (g) Reaction time (hr) Degree of polymerization (n) Molecular weight Solvent/Amount (g) (g) A HMDI 3.0 15 10 3.2 960 B HMDI 3.0 15 15 10.5 2551 C IPDI 3.0 15 12 3.1 775 D IPDI 3.0 15 16 10.2 2041 E TMXDI 3.0 60 10 3.5 944 F TMXDI 3.0 60 15 12.1 2664 G TIDI 3.0 3 7 2.9 966 H TIDI 3.0 3 15 9.7 2657 I MDI 1.0 0.5 4 5.2 1323 THF/900 Solid content 8.66 wt.% J MDI 1.0 1 2 10.7 2457 THF/900 Solid content 8.54 wt.% K TDI 1.0 0.5 4 4.6 7730 Perclene/900 Solid content 8.09 wt.% L TDI 1.0 1 3 12.0 1736 Perclene/900 Solid content 7.85 wt.% In Table 1, the abbreviations of diisocyanates have the following meanings, and the degree of polymerization and molecular weight were calculated from NCO % determined by a titration method: HMDI: 4,4'-Dicyclohexylmethane diisocyanate TMXDI: Tetramethylxylylene diisocyanate IPDI: Isophorone diisocyanate MDI: 4,4'-Diphenylmethane diisocyanate TDI: Tolylene diisocyanate TIDI: Triisopropylidenephenyl diisocyanate Example 1 To 96 g of the carbodiimide-modified diisocyanate of Synthesis No. A were added 50 g of toluene and 23.2 g of 2-hydroxyethyl acrylate (a double bond compound) corresponding to one equivalent of isocyanate, and they were subjected to reaction at 95°C for 5 hours while being stirred at 200 rpm using a mechanical stirrer, to synthesize a carbodiimide having double bonds and a molecular weight of 1,260 [the styrene-reduced molecular weight as measured by gel permeation chromatography (GPC) (the same applies to Examples appearing hereinafter)]. Examples 2 to 27 In the same manner as in Example 1, except that the kind and amount of the double bond compound were changed as shown in Table 2, carbodiimides having double bonds and having the molecular weights shown in Table 2 were synthesized. Examples 28 to 54 In the same manner as in Examples 1 to 27, except that the solvent was not used, carbodiimides having double bonds and having the molecular weights shown in Table 2 were synthesized. Example No. Double-bond compd. Amount (g) Molecular weight Example No. Double-bond compd. Amount (g) Molecular weight 1 DBC-1 23.2 1260 28 DBC-1 23.2 1260 2 DBC-2 26.0 1290 29 DBC-2 26.0 1290 3 DBC-3 26.0 1310 30 DBC-3 26.0 1310 4 DBC-4 28.8 1320 31 DBC-4 28.8 1320 5 DBC-5 59.7 1600 32 DBC-5 59.7 1600 6 DBC-6 62.4 1700 33 DBC-6 62.4 1700 7 DBC-7 25.6 1260 34 DBC-7 25.6 1260 8 DBC-8 28.4 1270 35 DBC-8 28.4 1270 9 DBC-9 11.6 1160 36 DBC-9 11.6 1160 10 DBC-10 14.4 1180 37 DBC-10 14.4 1180 11 DBC-11 17.2 1190 38 DBC-11 17.2 1190 12 DBC-14 19.8 1200 39 DBC-14 19.8 1200 13 DBC-15 19.4 1190 40 DBC-15 19.4 1190 14 DBC-16 27.8 1270 41 DBC-16 27.8 1270 15 DBC-18 19.6 2200 42 DBC-18 19.6 2200 16 DBC-19 25.2 1250 43 DBC-19 25.2 1250 17 DBC-20 22.8 1220 44 DBC-20 22.8 1220 18 DBC-21 26.8 1250 45 DBC-21 26.8 1250 19 DBC-22 20.4 1180 46 DBC-22 20.4 1180 20 DBC-23 51.3 1490 47 DBC-23 51.3 1490 21 DBC-24 70.0 1970 48 DBC-24 70.0 1970 22 DBC-25 100.0 2190 49 DBC-25 100.0 2190 23 DBC-26 74.0 1720 50 DBC-26 74.0 1720 24 DBC-27 32.4 1700 51 DBC-27 32.4 1700 25 DBC-28 90.0 2290 52 DBC-28 90.0 2290 26 DBC-29 45.6 2030 53 DBC-29 45.6 2030 27 DBC-30 84.0 1990 54 DBC-30 84.0 1990 In Table 2, the symbols of the double-bond compounds have the following meanings (the same applies to Examples appearing hereinafter): DBC-1: 2-Hydroxyethyl acrylate DBC-2: 2-Hydroxyethyl methacrylate DBC-3: 2-Hydroxypropyl acrylate DBC-4: 2-Hydroxypropyl methacrylate DBC-5: Pentaerythritol triacrylate DBC-6: Pentaerythritol trimethacrylate DBC-7: Glycidyl acrylate DBC-8: Glycidyl methacrylate DBC-9: Allyl alcohol DBC-10: 3-Buten-1-ol DBC-11: 4-Penten-1-ol DBC-12: Allylamine DBC-13: N-methylallylamine DBC-14: N-ethyl-2-methylallylamine DBC-15: Diallylamine DBC-16: Allylcyclohexylamine DBC-17: Butadiene monoxide DBC-18: 1,2-Epoxy-5-hexene DBC-19: 1,2-Epoxy-7-octene DBC-20: Allyl glycidyl ether DBC-21: 2-Allylphenol DBC-22: 2-Allyloxyethanol DBC-23: Pentaerythritol triallyl ether DBC-24: Polyethylene glycol monomethacrylate DBC-25: Polypropylene glycol monomethacrylate DBC-26: Polyethylene glycol monoacrylate DBC-27: 2-Sulfoethyl methacrylate DBC-28: Polyethylene glycol monoacrylate DBC-29: 2-Hydroxy-1,3-dimethacryloxypropane DBC-30: Polypropylene glycol monoacrylate Examples 55 to 81 In the same manner as in Examples 28 to 54, except that the carbodiimide-modified diisocyanate was replaced by 255.1 g of that of Synthesis No. B, carbodiimides having double bonds and having the molecular weights shown in Table 3 were synthesized. Examples 82 to 108 In The same manner as in Examples 28 to 54, except that the carbodiimide-modified diisocyanate was replaced by 77.5 g of that of Synthesis No. C, carbodiimides having double bonds and having the molecular weights shown in Table 3 were synthesized. Example No. Double-bond compd. Amount (g) Molecular weight Example No. Double-bond compd. Amount (g) Molecular weight 55 DBC-1 23.2 2960 82 DBC-1 23.2 1060 56 DBC-2 26.0 2980 83 DBC-2 26.0 1090 57 DBC-3 26.0 3010 84 DBC-3 26.0 1120 58 DBC-4 28.8 2990 85 DBC-4 28.8 1130 59 DBC-5 59.7 3260 86 DBC-5 59.7 1410 60 DBC-6 62.4 3380 87 DBC-6 62.4 1500 61 DBC-7 25.6 2910 88 DBC-7 25.6 1060 62 DBC-8 28.4 2890 89 DBC-8 28.4 1080 63 DBC-9 11.6 2900 90 DBC-9 11.6 960 64 DBC-10 14.4 2890 91 DBC-10 14.4 980 65 DBC-11 17.2 2890 92 DBC-11 17.2 1000 66 DBC-14 19.8 2860 93 DBC-14 19.8 1010 67 DBC-15 19.4 2830 94 DBC-15 19.4 990 68 DBC-16 27.8 2910 95 DBC-16 27.8 1080 69 DBC-18 19.6 3860 96 DBC-18 19.6 2000 70 DBC-19 25.2 2910 97 DBC-19 25.2 1060 71 DBC-20 22.8 2860 98 DBC-20 22.8 1030 72 DBC-21 26.8 2880 99 DBC-21 26.8 1060 73 DBC-22 20.4 2810 100 DBC-22 20.4 990 74 DBC-23 51.3 3100 101 DBC-23 51.3 1300 75 DBC-24 70.0 4070 102 DBC-24 70.0 1720 76 DBC-25 100.0 4160 103 DBC-25 100.0 1960 77 DBC-26 74.0 3350 104 DBC-26 74.0 1530 78 DBC-27 32.4 3970 105 DBC-27 32.4 1430 79 DBC-28 90.0 4610 106 DBC-28 90.0 2030 80 DBC-29 45.6 4640 107 DBC-29 45.6 1730 81 DBC-30 84.0 3900 108 DBC-30 84.0 1770 Examples 109 to 135 In the same manner as in Examples 28 to 54, except that the carbodiimide-modified diisocyanate was replaced by 204.1 g of that of Synthesis No. D, carbodiimides having double bonds and having the molecular weights shown in Table 4 were synthesized. Example No. Double-bond compound Amount (g) Molecular weight 109 DBC-1 23.2 2420 110 DBC-2 26.0 2440 111 DBC-3 26.0 2470 112 DBC-4 28.8 2460 113 DBC-5 59.7 2730 114 DBC-6 62.4 2840 115 DBC-7 25.6 2380 116 DBC-8 28.4 2370 117 DBC-9 11.6 2340 118 DBC-10 14.4 2340 119 DBC-11 17.2 2340 120 DBC-14 19.8 2330 121 DBC-15 19.4 2300 122 DBC-16 27.8 2380 123 DBC-18 19.6 3330 124 DBC-19 25.2 2380 125 DBC-20 22.8 2340 126 DBC-21 26.8 2360 127 DBC-22 20.4 2290 128 DBC-23 51.3 2580 129 DBC-24 70.0 3400 130 DBC-25 100.0 3530 131 DBC-26 74.0 2830 132 DBC-27 32.4 3240 133 DBC-28 90.0 3870 134 DBC-29 45.6 3800 135 DBC-30 84.0 3290 Examples 136 to 165 In the same manner as in Examples 28 to 54, except that the carbodiimide-modified diisocyanate was replaced by 94.4 g of that of Synthesis No. E, the double bond compound was replaced by those shown in Table 5 in the amounts shown in Table 5 and the reaction was carried out at 50°C for 8 hours (in Examples 147 to 151, for 3 hours), carbodiimides having double bonds and having the molecular weights shown in Table 5 were synthesized. Example Nos. 166 to 195 In the same manner as in Example Nos. 136 to 165, except that the carbodiimide-modified diisocyanate was replaced by 266.4 g of that of Synthesis No. F (provided that when the double bond compounds DBC-12 - DBC-16 were used, the reaction time was 3 hours and in the other cases, the reaction time was 8 hours), carbodiimides having double bonds and having the molecular weights shown in Table 5 were synthesized. Example No. Double-bond compd. Amount (g) Molecular weight Example No. Double-bond compd. Amount (g) Molecular weight 136 DBC-1 23.2 1240 166 DBC-1 23.2 3080 137 DBC-2 26.0 1270 167 DBC-2 26.0 3110 138 DBC-3 26.0 1300 168 DBC-3 26.0 3130 139 DBC-4 28.8 1310 169 DBC-4 28.8 3110 140 DBC-5 59.7 1580 170 DBC-5 59.7 3380 141 DBC-6 62.4 1680 171 DBC-6 62.4 3500 142 DBC-7 25.6 1240 172 DBC-7 25.6 3030 143 DBC-8 28.4 1250 173 DBC-8 28.4 3010 144 DBC-9 11.6 1150 174 DBC-9 11.6 3020 145 DBC-10 14.4 1160 175 DBC-10 14.4 3010 146 DBC-11 17.2 1180 176 DBC-11 17.2 3010 147 DBC-12 11.4 1160 177 DBC-12 11.4 3050 148 DBC-13 14.2 1170 178 DBC-13 14.2 3030 149 DBC-14 19.8 1180 179 DBC-14 19.8 2980 150 DBC-15 19.4 1170 180 DBC-15 19.4 2940 151 DBC-16 27.8 1250 181 DBC-16 27.8 3030 152 DBC-17 14.0 1170 182 DBC-17 14.0 3040 153 DBC-18 19.6 2180 183 DBC-18 19.6 3970 154 DBC-19 25.2 1240 184 DBC-19 25.2 3030 155 DBC-20 22.8 1200 185 DBC-20 22.8 2980 156 DBC-21 26.8 1230 186 DBC-21 26.8 2990 157 DBC-22 20.4 1170 187 DBC-22 20.4 2920 158 DBC-23 51.3 1470 188 DBC-23 51.3 3210 159 DBC-24 70.0 1950 189 DBC-24 70.0 4220 160 DBC-25 100.0 2170 190 DBC-25 100.0 4300 161 DBC-26 74.0 1710 191 DBC-26 74.0 3470 162 DBC-27 32.4 1670 192 DBC-27 32.4 4130 163 DBC-28 90.0 2270 193 DBC-28 90.0 4770 164 DBC-29 45.6 2000 194 DBC-29 45.6 4830 165 DBC-30 84.0 1970 195 DBC-30 84.0 4040 Examples 196 to 225 In the same manner as in Examples 136 to 165, except that the carbodiimide-modified diisocyanate was replaced by 96.6 g of that of Synthesis No. G (provided that when the double bond compounds DBC-12 - DBC-16 were used, the reaction time was 3 hours and in the other cases, the reaction time was 8 hours), carbodiimides having double bonds and having the molecular weights shown in Table 6 were synthesized. Examples 226 to 255 In the same manner as in Examples 136 to 165, except that the carbodiimide-modified diisocyanate was replaced by 265.7 g of that of Synthesis No. H (provided that when the double bond compounds DBC-12 - DBC-16 were used, the reaction time was 3 hours and in the other cases, the reaction time was 8 hours), carbodiimides having double bonds and having the molecular weights shown in Table 6 were synthesized. Example No. Double-bond compd. Amount (g) Molecular weight Example No. Double-bond compd. Amount (g) Molecular weight 196 DBC-1 23.2 1270 226 DBC-1 23.2 3080 197 DBC-2 26.0 1290 227 DBC-2 26.0 3100 198 DBC-3 26.0 1320 228 DBC-3 26.0 3120 199 DBC-4 28.8 1330 229 DBC-4 28.8 3110 200 DBC-5 59.7 1610 230 DBC-5 59.7 3370 201 DBC-6 62.4 1700 231 DBC-6 62.4 3500 202 DBC-7 25.6 1260 232 DBC-7 25.6 3020 203 DBC-8 28.4 1270 233 DBC-8 28.4 3000 204 DBC-9 11.6 1170 234 DBC-9 11.6 3010 205 DBC-10 14.4 1180 235 DBC-10 14.4 3000 206 DBC-11 17.2 1200 236 DBC-11 17.2 3000 207 DBC-12 11.4 1180 237 DBC-12 11.4 3040 208 DBC-13 14.2 1190 238 DBC-13 14.2 3020 209 DBC-14 19.8 1210 239 DBC-14 19.8 2970 210 DBC-15 19.4 1190 240 DBC-15 19.4 2940 211 DBC-16 27.8 1280 241 DBC-16 27.8 3020 212 DBC-17 14.0 1190 242 DBC-17 14.0 3030 213 DBC-18 19.6 2200 243 DBC-18 19.6 3970 214 DBC-19 25.2 1260 244 DBC-19 25.2 3020 215 DBC-20 22.8 1230 245 DBC-20 22.8 2970 216 DBC-21 26.8 1260 246 DBC-21 26.8 2990 217 DBC-22 20.4 1190 247 DBC-22 20.4 2910 218 DBC-23 51.3 1490 248 DBC-23 51.3 3200 219 DBC-24 70.0 1980 249 DBC-24 70.0 4210 220 DBC-25 100.0 2200 250 DBC-25 100.0 4290 221 DBC-26 74.0 1730 251 DBC-26 74.0 3460 222 DBC-27 32.4 1710 252 DBC-27 32.4 4120 223 DBC-28 90.0 2300 253 DBC-28 90.0 4760 224 DBC-29 45.6 2040 254 DBC-29 45.6 4810 225 DBC-30 84.0 2000 255 DBC-30 84.0 4030 Examples 256 to 285 In the same manner as in Examples 1 to 27, except that the carbodiimide-modified diisocyanate was replaced by 763.7 g of a solution of the carbodiimide-modified diisocyanate of Synthesis No. I in tetrahydrofuran (THF) and the double bond compound was replaced by one of the double bond compounds shown in Table 7 in the amount shown in Table 7, carbodiimides having double bonds and having the molecular weights shown in Table 7 were synthesized. Examples 286 to 315 In the same manner as in Examples 256 to 285, except that the carbodiimide-modified diisocyanate was replaced by 1,438.5 g of a solution of the carbodiimide-modified diisocyanate of Synthesis No. J in tetrahydrofuran (THF), carbodiimides having double bonds and having the molecular weights shown in Table 7 were synthesized. Example No. Double-bond compd. Amount (g) Molecular weight Example No. Double-bond compd. Amount (g) Molecular weight 256 DBC-1 11.6 1650 286 DBC-1 11.6 2860 257 DBC-2 13.0 1670 287 DBC-2 13.0 2880 258 DBC-3 13.0 1700 288 DBC-3 13.0 2910 259 DBC-4 14.4 1710 289 DBC-4 14.4 2900 260 DBC-5 29.8 1980 290 DBC-5 29.8 3160 261 DBC-6 31.2 2080 291 DBC-6 31.2 3290 262 DBC-7 12.8 1630 292 DBC-7 12.8 2820 263 DBC-8 14.2 1640 293 DBC-8 14.2 2800 264 DBC-9 5.8 1560 294 DBC-9 5.8 2790 265 DBC-10 7.2 1570 295 DBC-10 7.2 2790 266 DBC-11 8.6 1580 296 DBC-11 8.6 2790 267 DBC-12 5.7 1570 297 DBC-12 5.7 2820 268 DBC-13 7.1 1580 298 DBC-13 7.1 2810 269 DBC-14 9.9 1580 299 DBC-14 9.9 2760 270 DBC-15 9.7 1560 300 DBC-15 9.7 2730 271 DBC-16 13.9 1640 301 DBC-16 13.9 2810 272 DBC-17 7.0 1580 302 DBC-17 7.0 2820 273 DBC-18 9.8 2580 303 DBC-18 9.8 3760 274 DBC-19 12.6 1630 304 DBC-19 12.6 2820 275 DBC-20 11.4 1600 305 DBC-20 11.4 2770 276 DBC-21 13.4 1620 306 DBC-21 13.4 2780 277 DBC-22 10.2 1550 307 DBC-22 10.2 2710 278 DBC-23 25.6 1850 308 DBC-23 25.6 3000 279 DBC-24 35.0 2450 309 DBC-24 35.0 3950 280 DBC-25 50.0 2640 310 DBC-25 50.0 4050 281 DBC-26 37.0 2090 311 DBC-26 37.0 3250 282 DBC-27 16.2 2220 312 DBC-27 16.2 3840 283 DBC-28 45.0 2820 313 DBC-28 45.0 4470 284 DBC-29 22.8 2630 314 DBC-29 22.8 4490 285 DBC-30 42.0 2430 315 DBC-30 42.0 3790 Examples 316 to 345 In the same manner as in Examples 256 to 285, except that the carbodiimide-modified diisocyanate was replaced by 477.8 g of a solution of the carbodiimide-modified diisocyanate of Synthesis No. K in Perclene, carbodiimides having double bonds and having the molecular weights shown in Table 8 were synthesized. Examples 346 to 375 In the same manner as in Examples 256 to 285, except that the carbodiimide-modified diisocyanate was replaced by 1,105.7 g of a solution of the carbodiimide-modified diisocyanate of Synthesis No. I in Perclene, carbodiimides having double bonds and the molecular weights shown in Table 8 were synthesized. Example No. Double-bond compd. Amount (g) Molecular weight Example No. Double-bond compd. Amount (g) Molecular weight 316 DBC-1 11.6 8500 346 DBC-1 11.6 2090 317 DBC-2 13.0 8520 347 DBC-2 13.0 2110 318 DBC-3 13.0 8540 348 DBC-3 13.0 2140 319 DBC-4 14.4 8430 349 DBC-4 14.4 2140 320 DBC-5 29.8 8670 350 DBC-5 29.8 2410 321 DBC-6 31.2 8870 351 DBC-6 31.2 2520 322 DBC-7 12.8 8310 352 DBC-7 12.8 2070 323 DBC-8 14.2 8190 353 DBC-8 14.2 2060 324 DBC-9 5.8 8540 354 DBC-9 5.8 2010 325 DBC-10 7.2 8460 355 DBC-10 7.2 2010 326 DBC-11 8.6 8400 356 DBC-11 8.6 2020 327 DBC-12 5.7 8640 357 DBC-12 5.7 2030 328 DBC-13 7.1 8520 358 DBC-13 7.1 2020 329 DBC-14 9.9 8260 359 DBC-14 9.9 2010 330 DBC-15 9.7 8170 360 DBC-15 9.7 1990 331 DBC-16 13.9 8260 361 DBC-16 13.9 2070 332 DBC-17 7.0 8560 362 DBC-17 7.0 2030 333 DBC-18 9.8 9260 363 DBC-18 9.8 3010 334 DBC-19 12.6 8310 364 DBC-19 12.6 2060 335 DBC-20 11.4 8210 365 DBC-20 11.4 2020 336 DBC-21 13.4 8180 366 DBC-21 13.4 2040 337 DBC-22 10.2 8090 367 DBC-22 10.2 1970 338 DBC-23 25.6 8340 368 DBC-23 25.6 2270 339 DBC-24 35.0 10920 369 DBC-24 35.0 2990 340 DBC-25 50.0 10590 370 DBC-25 50.0 3150 341 DBC-26 37.0 8650 371 DBC-26 37.0 2520 342 DBC-27 16.2 11380 372 DBC-27 16.2 2810 343 DBC-28 45.0 12130 373 DBC-28 45.0 3420 344 DBC-29 22.8 13130 374 DBC-29 22.8 3300 345 DBC-30 42.0 10120 375 DBC-30 42.0 2920 Incidentally, the properties of the carbodiimides having double bonds of the present invention synthesized as mentioned above were as follows. Examples 1 to 27 Pale yellow liquid (solution) Examples 28 to 54 (excluding Examples 48, 49, 50, 52 and 54) and Examples 55 to 81 (excluding Examples 75, 76, 77, 79 and 81) Pale yellow solid having softening point of 35°C to 45°C Examples 82 to 108 (excluding Examples 102, 103, 104, 106 and 108) and Examples 109 to 135 (excluding Examples 129, 130, 131, 133 and 135) Page yellow solid having softening point of 35°C to 55°C Examples 136 to 195 Brown liquid having high viscosity Examples 196 to 225 (excluding Examples 219, 220, 221, 223, 225, 249, 250, 251, 253 and 255) Pale yellow solid having softening point of 45°C to 65°C Examples 256 to 375 Pale yellow liquid (solution) Examples 48, 49, 50, 52, 54, 75, 76, 77, 79, 81, 102, 103, 104, 106, 108, 129, 130, 131, 133, 135, 219, 220, 221, 223, 225, 249, 250, 251, 253 and 255 Pale yellow liquid having high viscosity Moreover, the structures of the carbodiimides having double bonds of the present invention were confirmed as follows. 1. IR The disappearance of the peak of isocyanate at 2200-2300 cm -1 was observed, whereby it was confirmed that the isocyanate had reacted quantitatively with an amount equivalent thereto of a group capable of reacting with the isocyanate group. Moreover, the peak of carbodiimide at 2100-2200 cm -1 was observed, and from the fact that carbodiimide group was present in the resulting compound and the ratio of the peak of carbodiimide to the C-H peak due to alkyl in the vicinity of 3000-3500 cm -1 had not changed, it was confirmed that no reduction of the amount of carbodiimide was seen and the theoretical amount of carbodiimide was present. Furthermore, in the Examples in which the double bond compounds DBC-7, 8, 17, 18, 19 and 20 were used, peaks resulting from reaction between epoxy and isocyanate were confirmed at 1700-1800 cm -1 , in Examples in which the double bond compounds DBC-1, 2, 3, 4, 5, 6, 9, 10, 11, 21, 22, 23, 24, 25, 26, 27, 28, 29 and 30 were used, peaks resulting from reaction between alcohol and isocyanate were confirmed at 1700-1800 cm -1 , and in the Examples in which the double bond compounds DBC-12, 13, 14, 15 and 16 were used, peaks resulting from reaction between amine and isocyanate were confirmed at 1400-1700 cm -1 . 2. NMR The proton of H 2 C=CH- or H 2 C=C(R)- was observed at 4.5-7 ppm. Further, the amount of proton bonded to the carbon of the double bond was calculated from the integration value of proton peak of methyl and/or methylene group in the molecule, whereby the presence of a theoretical amount of unsaturated bond was confirmed. Assay of hydrolysis stabilizing effect of the present carbodiimide having double bonds (1) A composition composed of the following components was injected in an amount of 20 g into a circle-shaped mold having a diameter of 50 mm and cured at 100°C for 6 hours. Unsaturated polyester resin (Polymal 6316, registered trade mark of Takeda Chemical Industries, Ltd.) 100 g Carbodiimide having double bonds synthesized in one of Examples 1 to 375 5 g Benzoyl peroxide (BPO) 1 g (2) In the same manner as above, a composition composed of the following components was injected in an amount of 20 g into a circle-shaped mold having a diameter of 50 mm and allowed to gel at 30°C for 2 hours and then cured at 50°C for 24 hours. Unsaturated polyester resin (Polyset 5595 PT-L, registered trade mark of Hitachi Chemical Co., Ltd.) 100 g Carbodiimide having double bonds synthesized in one of Examples 1 to 375 5 g Methyl ethyl ketone peroxide 1 g (3) In the same manner as in (1) and (2) above, except that the carbodiimide having double bonds synthesized in Examples 1 to 375 was not added, respective blanks were prepared. Each of the resin molded articles obtained under the above conditions was immersed in hot water of 90°C, and the state of the resin after 240 hours was visually observed to evaluate blister and cracking, thereby finding that the resin molded articles each containing the carbodiimide having double bonds synthesized in one of Examples 1 to 375 had a smooth surface and the blanks free from the carbodiimide had cracks on the surface and in the interior. Assay of effect of resin cross-linking of the present carbodiimide havinq double bonds (1) A blue pigment was added to an aqueous acrylic resin (Joncryl 61J, registered trade mark of JOHNSON & JOHNSON; acid value: 195; aqueous solution of a solid content of 30.5%), and thereto was further added one of the carbodiimides having double bonds synthesized in Examples 48, 49, 50, 52, 54, 75, 76, 77, 79, 81, 102, 103, 104, 106, 108, 129, 130, 131, 133, 135, 159, 160, 161, 163, 165, 189, 190, 191, 193, 195, 219, 220, 221, 223, 225, 249, 250, 251, 253, 255, 279, 280, 281, 283, 285, 309, 310, 311, 313, 315, 339, 340, 341, 343, 345, 369, 370, 371, 373 and 375 in an equivalent (the carboxylic acid of the resin and the carbodiimide group were in equivalent relation), and thereafter, the resulting mixture was formed into a PET film having a thickness of 100 µm by a bar coater and then the film was dried at 80 °C for 30 minutes to prepare a film having a thickness of 30 µm. (2) A blue pigment was added to an oily acrylic resin (Joncryl J586, registered trade mark of JOHNSON & JOHNSON; acid value: 105; a toluene solution having a solid content of 20%), and thereto was further added one of the carbodiimides having double bonds synthesized in Examples 1 to 375 in an equivalent (the carboxylic acid of the resin and the carbodiimide group were in equivalent relation), after which the resulting mixture was formed into a PET film having a thickness of 100 µm by a bar coater. The film was dried at 100°C for 10 minutes to prepare a film having a thickness of 20 µm. (3) In the same manner as in (1) and (2) above, except that the carbodiimide having double bonds was not added, respective blanks were prepared. Each of the films obtained as mentioned above was lightly rubbed with absorbent wadding impregnated with 28% ammonia (solvent A) or a water-methanol (4/6) mixture (solvent B) to examine the number of rubbing strokes until crocking was caused, to find that each film containing the present carbodiimide having double bonds did not cause crocking even when rubbed more than 100 strokes with each of the absorbent waddings impregnated with solvents, in both cases of the aqueous and oily resins. However, in the case of the oily resin film free from the present carbodiimide having double bonds, the number of rubbing strokes for crocking was 20 in the case of solvent A and 5 in the case of solvent B. Similarly, in the aqueous resin film free from the present carbodiimide having double bonds, the number of rubbing strokes for crocking was 3 in the case of solvent A and 1 in the case of solvent B. The present carbodiimide having double bonds is represented by the formula (1): R 1 -X-(R 2 -NCN) n -R 2 -X-R 3 and this carbodiimide exhibits excellent performance as a hydrolysis stabilizer for ester bond-containing resins or as a cross-linking agent for resins having a group capable of reacting with carbodiimide group or for compounds having an olefinic double bond(s).

Claims: A carbodiimide having double bonds, which is represented by the formula (1): R 1 -X-(R 2 -NCN) n -R 2 -X-R 3 wherein R 1 and R 3 may be the same as or different from each other and each represents the organic residue having 3 to 40 carbon atoms, of a compound having at least one olefinic double bond and a functional group capable of reacting with an isocyanate group, formed by removing the functional group therefrom; R 2 represents the organic residue of a diisocyanate formed by removing the isocyanate group therefrom; plural R 2 groups may be different from one another; X represents a functional group formed by reaction between the above isocyanate group and the above functional group capable of reacting with isocyanate group; and n is a numerical value between 1.0 and 20.0. The carbodiimide having double bonds according to claim 1, wherein R 2 is the organic residue resulting from 4,4' - dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate or isophorone diisocyanate. The carbodiimide having double bonds according to claim 1, wherein R 2 is the organic residue resulting from 4,4' - diphenylmethane diisocyanate, tolylene diisocyanate or triisopropylidenephenyl diisocyanate. The carbodiimide having double bonds according to claim 1, wherein at least one of R 1 and R 3 is the organic residue resulting from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, glycidyl acrylate, glycidyl methacrylate, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, allylamine, N-methylallylamine, N-ethyl-2-methylallylamine, diallylamine, allylcyclohexylamine, butadiene monoxide, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, allyl glycidyl ether, 2-allylphenol, 2-allyloxyethanol, pentaerythritol triallyl ether, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monoacrylate, 2-sulfoethyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane or polypropylene glycol monoacrylate. A hydrolysis stabilizer for an ester bond-containing resin, which comprises as a main component a carbodiimide according to one of the claims 1 - 4. The hydrolysis stabilizer according to claim 5, wherein the ester bond-containing resin is a polyester resin or a polyesterpolyurethane resin. A cross-linking agent for a resin having a group capable of reacting with carbodiimide group, which comprises as a main component a carbodiimide according to one of the claims 1 - 4. A cross-linking agent for a compound having an olefinic double bond(s), which comprises as a main component a carbodiimide according to one of the claims 1 - 4.

Inventors: HORIE NAOFUMI, IMASHIRO YASUO, TAKAHASHI IKUO, YAMANE TAKESHI, HORIE, NAOFUMI, IMASHIRO, YASUO, TAKAHASHI, IKUO, YAMANE, TAKESHI
Applicants: NISSHIN SPINNING, NISSHINBO INDUSTRIES, INC.
Application year: 1997
Main classification: C07C267
IPC codes: C07C267, C08K5