Fluoroalkylated allylurethane, its copolymer and water- and oil-repellent, anti-soiling processing agent containing the copolymer as an effective component

Abstract: A fluoroalkylated allylurethane represented by the following general formula: RfROCONHR'NHCOOC n H 2n OCH 2 CH=CH 2 where Rf is a perfluoroalkyl group having 2 to 20 carbon atoms, R is a divalent organic group, R' is a diisocyanate residue, and n is an integer of 2 to 6, can undergo emulsion polymerization with at least one of a methacrylate ester, an acrylate ester and vinylidene chloride to give an effective aqueous copolymer emulsion for a water- and oil-repellent, anti-soiling processing agent.

Description: 1. FIELD OF THE INVENTION The present invention relates to a novel fluoroalkylated allylurethane, its copolymer and a water- and oil-repellent, anti-soiling processing agent containing the copolymer as an effective component, and more particularly to a copolymer capable of forming a water- and oil- repellent, which can give a distinguished water- and oil- repellency and a distinguished anti-dry soiling property for fibers, particularly carpets and a novel fluoroalkylated allylurethane as a comonomer component for the copolymer. 2. RELATED ART Various fluorinated polymers have been so far known as water- and oil- repellents for fibers. For example, JP-B-47-6600 (corresponding to DE 1 795 261) discloses that bulk homopolymerization products of yellowish viscous oil obtained by reaction of tolylenediisocyanate (a mixture consisting of about 80% of 2,4-isomer and about 20% 2,6-isomer) with fluoroalcohol (C 17 F 35 CH 2 OH), followed by reaction with allyl alcohol show a distinguished water- and oil- repellency for natural fibers. However, such viscous oil-like monomers undergo solution polymerization because of its good solubility in an organic solvent, but their emulsification is too hard and thus no aqueous emulsion can be obtained in case of the emulsion polymerization, resulting in formation of precipitates during the polymerization. JP-B-3-4542 (corresponding to EP 225 826) discloses that (co)polymers for the protection of leathers can be obtained by solution polymerization from fluorinated acryl monomers prepared by reaction of 2,4-tolylenediisocyanate with fluoroalcohol (C 6 F 13 CH 2 CH 2 OH), followed by reaction with 2-hydroxyethyl methacrylate, but the fluorinated acryl monomers are poor in emulisifability and thus their emulsion polymerization is also hard to conduct. JP-A-3-76873 (corresponding to EP 414 155) discloses an anti-soiling processing agent obtained by emulsion polymerization between fluorourethane acrylate, prepared by reaction of triisocyanate (e.g. hexamethylenediisocyanate trisbiuret) with fluoroalcohol (e.g. C 9 F 19 CH 2 CH 2 OH), followed by reaction with hydroxylated methacrylate ester [e.g. CH 2 =C(CH 3 )COO(CH 2 CH 2 O)nH], and methyl methacrylate or the like. However, pretreatments must be carried out before the emulsion polymerization, i.e. first emulsification by a high-speed, rotating homomixer and second emulsification by a high pressure homogenizer. Thereafter, the emulsion polymerization reaction is to be carried out. As mentioned above, fluorourethane has problems of difficult emulsification and formation of precipitates during the emulsion polymerization based on the ordinary emulsification process, and thus there is an additional problem of necessity for use of an expensive emulsification apparatus as an emulsification means. GB 1,102,903 provides fluorine-containing compounds having a group of the formula n being an integer from 2 to 20 inclusive and m being 0 or an integer from 1 to 20 inclusive, bonded to one end position. The compounds are used in water-repellent and oil-repellent compositions. EP-A-0 103 752 discloses a stainproofing agent containing as an active ingredient a polyfluoroalkyl group-containing compound represented by the following general formula and having a molecular weight of from 800 to 3000: where R 1 is a polyfluoroalkyl group having from 1 to 20 carbon atoms, X is -R-, -CON(R 1 )-Q- or -SO 2 N(R 1 )-Q- (where R is a divalent alkylene group, R 1 is a hydrogen atom or a lower alkyl group and Q is a divalent organic group), each of A and A' is -O-, -S- or -N(Z')- (where Z' is a hydrogen atom or a monovalent organic group), Z is a monovalent organic group, W is a trivalent organic group, a is an integer of 1, 2 or 3. SUMMARY OF THE INVENTION An object of the present invention is to provide a copolymer capable of forming a water- and oil- repellent, anti-soiling processing agent; which can give a distinguished water-and oil- repellency and a distinguished anti-dry soiling property for fibers, particularly carpets, etc., which can be obtained in an aqueous emulsion by the ordinary emulsion polymerization method and also to provide a novel fluoroalkylated allylurethane as a comonomer component for the copolymer. According to the present invention, there is provided a novel fluoroalkylated allylurethane represented by the following general formula: RfROCONHR' NHCOOC n H 2n OCH 2 CH=CH 2 where Rf is a perfluoroalkyl group having 2 to 20 carbon atoms; R is a divalent organic group; R' is a diisocyanate residue; and n is an integer of 2 to 6. The present novel fluoroalkylated allylurethane can give an aqueous emulsion of copolymer useful as an effective water - and oil- repellent, anti-soiling processing agent by emulsion polymerization with at least one of a methacrylate ester, acrylate ester and vinylidene chloride. DETAILED DESCRIPTION OF THE INVENTION The present novel fluoroalkylated allylurethane represented by the above general formula can be prepared by (1) reaction of a diisocyanate compound having two NCO groups of different reactivity in the molecule with a fluoroalcohol represented by the following general formula RfROH, where Rf and R have the same meanings as defined above, followed by reaction with alkyleneglycol monoallyl ether or by (2) reaction of a diisocyanate having two NCO groups of different reactivity in the molecule with alkyleneglycol monoallyl ether, followed by reaction with fluoroalcohol. In these individual reactions, the diisocyanate may offer different sites of substitution with the counterpart reactants, depending upon the sequence of adding equimolar amounts of the counterpart reactants to the diisocyanate, but the difference in the site of substitution on the diisocyanate gives no significant difference to properties of water- and oil-repellent, anti-soiling processing agent containing copolymers of the present fluoroalkylated allylurethane. Diisocyanate compounds each having two NCO groups of different reactivity in the molecule such as aromatic diisocyates (e.g. 2,4-tolylenediisocyanate, etc.) and alicyclic diisocyates (e.g. 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, etc.) can be used in the present invention as the diisocyanate compound. When a diisocyanate compound having NCO groups of same reactivity is used, there is a high possibility of formation of difluorourethane or diallylurethane, and the desired fluoroalkylated allylurethane will be hard to obtain. Fluoroalcohols whose Rf group is a straight or branched perfluoroalkyl group having 2 to 20 carbon atoms and whose R group is a straight or branched alkylene group of C m H 2m , where m is an integer of 2 to 6, a SO 2 NR 1 CH 2 CH 2 group, where R 1 is a lower alkyl group having 1 to 5 carbon atoms, a CON(C 2 H 5 )CH 2 CH 2 group, a CON(CH 3 )CH 2 CH 2 group, a CH 2 CH(OH)CH 2 group, etc. can be used in the present invention as the fluoroalcohol. Preferably, a fluoroalcohol whose Rf group is a straight perfluoroalkyl group having 6 to 16 carbon atoms and whose R group is a CH 2 CH 2 group is used in the present invention. Alkyleneglycol monoallyl ether for use in the present invention includes, for example, ethyleneglycol monoallyl ether, propyleneglycol monoallyl ether, butyleneglycol monoallyl ether, etc. Preferably, ethyleneglycol monoallyl ether is used in the present invention from the viewpoint of anti-dry soiling property. Reaction of the diisocyanate compound, the fluoroalcohol and the alkyleneglycol monoallyl ether can be carried out in an inert organic solvent or a polymerizable monomer. The inert organic solvent includes, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. esters such as ethyl acetate, butyl acetate, methyl propionate, methyl acetate,etc. and aromatic hydrocarbons such as toluene, etc. As the polymerizable monomer, those having no active hydrogen can be used. Preferably, such comonomer counterpart of fluoroalkylated allylurethane as a reaction product of the diisocyanate compound, the fluoroalcohol and the alkyleneglycol monoallyl ether as methacrylate esters, acrylate esters or vinylidene chloride is used. The methacrylate ester for use in the present invention includes, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, stearyl methacrylate, etc. The acrylate esters for use in the present invention are acrylates corresponding to the above-mentioned methacrylates. When the amount of the solvent, is too small, it will be difficult to control heat generation due to the exothermic reaction, whereas too a large amount of the solvent makes the reaction inefficient. From these viewpoints, about 0.5 to about 10 parts by weight, preferably about 0.5 to about 2 parts by weight of the solvent is used per one part by weight of the fluoroalcohol. A catalyst is used in the reaction. The calalyst includes, for example, an organotin compound such as dibutyl tin dilaurate, dibutyl tin maleate, dimethyldichloro tin, etc., a tertiary amine such as triethylamine, tripropylamine, tributylamine, etc., manganese, cobalt, zirconium, lead, barium nitrate, etc. Preferably, dibutyl tin maleate is used from the viewpoint of reaction rate, etc. The reaction using the catalyst is carried out at room temperature or higher, preferably about 40° to about 100°C. The above-mentioned reaction (1) can be carried out in the following manner: A diisocyanate compound, a catalyst and a solvent are charged into a reactor, and then a fluoroalcohol solution in a solvent is dropwise added thereto, or a diisocyanate compound and a catalyst are charged into a reactor and then a fluoroalcohol solution in a solvent is dropwise added thereto. When the Rf group of fluoroalcohol has 8 or more carbon atoms, the fluoroalcohol is in a solid state and thus dropwise addition as a solution in the solvent is carried out, whereas when the Rf group has 6 or less carbon atoms, the fluoroalcohol is in a liquid state and can be directly dropwise added thereto without its dissolution in the solvent. Rate of dropwise addition depends upon a reaction scale, a reactor size, etc., but too a high rate of dropwise addition may cause runaway of reaction because of the exothermic reaction. Thus, it is desirable to conduct dropwise addition slowly, while monitoring the reaction temperature. After the dropwise addition of fluoroalcohol, aging is carried out for about 0.1 to about 1 hour, and a vibration absorption of NCO can be observed at 2270 cm -1 by infrared spectroscopic analysis of the reaction solution. Thereafter, alkyleneglycol monoallyl ether is dropwise added thereto to completely consume NCO. When the urethanization reaction is completed, the absorption at 2270 cm -1 disappears completely. To prevent polymerization reaction of the product, it is preferable to conduct dropwise addition of alkylglycol monoallyl ether by adding about 300 to about 1,000 ppm of a polymerization inhibitor such as hydroquinone, etc. (on the basis of fluoroalcohol) to the alkylglycol monoallyl ether through its dissolution into the allkylglycol monoallyl ether. The above-mentioned reaction (2) can be carried out substantially in the same manner as the reaction (1). However, the reaction product of reaction (2) is different from that of reaction (1), as mentioned above. For example, in case of reaction of 2,4-tolylenediisocyanate with fluoroalcohol and alkyleneglycol monoallyl ether, the fluoroalcohol undergoes addition and substitution at the 4-position in the reaction (1), but on the 2-position in the reaction (2), and the alkyleneglycol monoallyl ether undergoes addition and substitution at the 2-position in the reaction (1), but at the 4-position in the reaction (2). The fluoroalkylated allylurethane as a product of these reactions can be copolymerized with at least one of a methacrylate ester, a acrylate ester and vinylidene chloride as mentioned above. These polymerizable monomer as comonomer may be added to the fluoroalkylated allylurethane, for the first time, at the stage of polymerization reaction or the polymerizable monomer used as a solvent for preparation of the fluoroalkylated allylurethane can be used as such. In the copolymerization reaction, an acrylic monomer having a cross-linkable group such as acrylamide, N-methylolacrylamide, N-(methoxymethyl)acrylamide, N-(butoxymethyl)acrylamide, glycidyl acrylate, glycidyl methacrylate, etc. can be also copolymerized. About 30 to about 90% by weight, preferably about 45 to about 80% by weight, of the fluoroalkylated allylurethane can be used on the basis of sum total of comonomers. Since the copolymerization proceeds substantially quantitatively, the charging proportions of the comonomers perse correspond to copolymerization proportion. From the viewpoint that hard copolymers are preferable to soft copolymers to give an anti-dry soiling property, in other words, copolymers having a higher Tg than room temperature are preferable, it is desirable to use at least two polymerizable monomers rather than a single polymerizable monomer. The acrylic monomer having a cross-linkable group can be used in a proportion of not more than about 10% by weight, preferably about 0.1 to about 5% by weight on the basis of sum total of comonomers. It is preferable from the viewpoint of use of the copolymers, (i.e. water- and oil-repellent, anti-soiling processing agent) to conduct copolymerization reaction by emulsion polymerization. Any of nonionic, cationic, anionic and amphoteric surfactants can be used as an emulsifying agent for the emulsion polymerization. Specifically, the emulsifying agent includes nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc., cationic surfactants such as quaternary ammonium salts, etc., anionic surfactants such as sodium laurylsulfate, ammonium laurylsulfate, sodium dodecylbenzenesulfonate, etc., and amphoteric surfactants such as lauryl betaine, stearyl betaine, etc. From the viewpoint of stability of simultaneous use of other chemicals for fiber treatment when the copolymers are used as an anti-soiling processing agent, the nonionic surfactants having a good stability with anionic or cationic chemicals are most preferable. Any polymerization catalyst can be used, so long as it is water-soluble. Preferable are ammonium persulfate, potassium persulfate, 2,2'-azobis(2-amidinopropane) dihydrochloride, etc. When the polymerization catalyst is used together with a reducing agent to form a redox system, the polymerization initiation temperature is lowered. That is, the polymerization can be initiated at about 20°C, generally at about 30°C, but the upper limit temperature is not more than 100°C, because an aqueous medium is used. An aqueous emulsion resulting from the copolymerization reaction has a solid concentration of about 20 to about 30% by weight. When the aqueous emulsion is used as a water- and oil-repellent, anti-soiling agent, it is diluted to a solid concentration of about 0.2 to about 2% by weight. The water- and oil-repellent, anti-soiling processing agent containing the present copolymer as an effective component can be effectively applied to fiber products, particularly carpets by such means as spraying, dipping, foam application, etc., followed by drying at a temperature of about 105° to about 140°C for about 1 to about 30 minutes. The present invention provides a novel fluoroalkylated allylurethane which can be copolymerized with at least one of methacrylate esters, acrylate esters and vinylidene chloride by emulsion polymerization. Emulsion polymerization can be readily carried out by an ordinary emulsification means. The resulting copolymers can give a distinguished water- and oil-repellency and a distinguished anti-dry soiling property for fiber products such as carpets, etc. PREFERRED EMBODIMENTS OF THE INVENTION The present invention will be described in detail below, referring to Examples. EXAMPLE 1 174g (one mole) of 2,4-tolylenedusocyanate, 1.6g of dibutyl tin dilaurate and 666g of MIBK (methyl isobutyl ketone) were charged into a separable glass flask with a stirrer, and the flask inside temperature was started to increase while stirring the mixture solution. When the inside temperature reached 50°C, 504g (one mole) of fluoroalcohol RfC 2 H 4 OH (average molecular weight: 504; Rf: a perfluoroalkyl group having an average carbon atom number of 8.8) as dissolved in 506g of MIBK was dropwise added to the mixture solution, while monitoring the inside temperature. When the inside temperature was slowly elevated to 70°C due to heat generation, the rate of dropwise addition was adjusted to keep that temperature. Time required from the start to the end of dropwise addition was 3 hours. After the dropwise addition, the reaction solution was subjected to aging for 30 minutes, and then a small amount of the reaction solution was sampled for infrared spectroscopic analysis. Absorption due to the absorption of -NCO was observed at 2270 cm -1 . 102g (one mole) of ethyleneglycol monoallyl ether dissolving 0.4g of hydroquinone was slowly dropwise added to the reaction solution so as not to cause abrupt heat generation. Rate of dropwise addition was adjusted to keep the reaction temperature at 70°C. Time required for the dropwise addition was 3 hours. After aging for one hour, a small amount of the reaction solution was sampled for infrared spectroscopic analysis. It was found that the absorption at 2270 cm -1 due to the absorption of -NCO disappeared. The reaction solution was 1934g of a clear dark brown fluoroalkylated allylurethane solution in MIBK. The reaction yield calculated from the solid concentration (40% by weight) was 99%. A portion of the MIBK solution was sampled and the solvent was distilled off from the sample. Brownish solid residue was determined for the melting point (no constant melting point is shown due to a mixture of perfluoroalkyl groups having different carbon atom numbers) and also for infrared absorption spectra (IR absorption) and nuclear magnetic resonances. The results are given below: Melting point: 80-86°C IR absorption: 1700 cm -1 (-NHCOO-) 1100-1300 cm -1 (-CF) 1 H-NMR(CD 3 COCD 3 ): 19 F-NMR(CD 3 COCD 3 ): Chemical shift(CFCl 3 ∼) F number a -80.13 3 b -125.16 2 c -120.58∼-122.44 11.6 d -112.35 2 (Total 18.6) EXAMPLES 2 TO 10 A corresponding amount of the fluoroalkylated allylurethane solution in MIBK obtained in Example 1 to the solid weight calculated from the solid concentration was weighed out and charged into a separable glass flask with a stirrer together with a given amount of MMA (methyl methacrylate), VdCl 2 (vinylidene chloride) or BzA (benzyl acrylate) as monomer (a) and a given amount of iBMA (isobutyl methacrylate), EMA (ethyl methacrylate) or MMA as monomer (b). Then, the following compounds were further charged therein: Polyoxyethylene nonylphenyl ether (Emulgen 950, a trademark of nonionic surfactant commercially available from Kao Corp., Japan) 3.3g n-Dodecyl mercaptan 0.25g Water (Example 2) 307.5g " (Example 3) 295g " (Examples 4 to 10) 270g the mixture was emulsified by a high speed rotating homomixer (Ultra-talax T25, tradename of a mixer commercially available from IKA, Japan) at 13000 rpm for 5 minutes. Thereafter, the flask was flushed with a nitrogen gas for 30 minutes with stirring. After elevation of the flask inside temperature to 40°C by heating, a given amount of N-MAM (N-methylol acrylamide), M-MAM (N-methoxymethyl acrylamide) or ACM (acrylamide) (not used in Examples 4 and 5), and an aqueous solution containing 2g of 2,2'-azobis(2-amidinopropane) dihydrochloride (V-50, a trademark of a product commercially available from Wako Junyaku K.K., Japan) dissolved in 30g of water were added to the reaction system, followed by polymerization reaction at 70°C for 4 hours. Stable, milky-white, aqueous emulsions each having a solid concentration of 25% by weight were obtained in all the Examples. Example No. Fluoroalkylated allylurethane Solid amount (g) Copolymerizable monomer (g) (a) (b) (c) 2 45 MMA 30 i BMA 23 N-MAM 2 3 50 MMA 37 iBMA 11 N-MAM 2 4 60 MMA 30 i BMA 10 - 5 60 MMA 30 EMA 10 - 6 60 MMA 30 EMA 9 M-MAM 1 7 60 MMA 20 EMA 19 M-MAM 1 8 60 MMA 30 EMA 9 ACM 1 9 60 VdCl 2 20 MMA 19 ACM 1 10 60 BzA 30 EMA 9 ACM 1 EXAMPLE 11 17.4g (0.1 mole) of 2,4-tolylenediisocyanate and 0.16g of dibutyl tin dilaurate were charged into a separable glass flask with a stirrer, and the flask inside temperature was started to increase, while stirring the mixture. When the inside temperature reached to 50°C, 50.4g (0.1 mole) of fluoroalcohol RfC 2 H 4 OH (average molecular weight: 504; Rf: a perfluoroalkyl group having an average carbon atom number of 8.8) as dissolved in 39g of MMA and 13g of EMA was dropwise added to the mixture solution slowly, while monitoring the inside temperature. When the inside temperature was slowly elevated to 70°C due to the exothermic reaction, the rate of dropwise addition was adjusted so as to keep that temperature. Time required from the start to the end of the dropwise addition was one hour. After the dropwise addition, the reaction solution was subjected to aging for 30 minutes and then a small amount of the reaction solution was sampled and subjected to infrared spectroscopic analysis. Absorption due to -NCO absorption was observed at 2270 cm -1 . Then, 10.2g (0.1 mole) of ethyleneglycol monoallyl ether dissolving 0.04g of hydroquinone was slowly dropwise added to the reaction solution so as not to cause vigorous heat generation. Rate of dropwise addition was adjusted to keep the reaction temperature at 70°C. Time required for the dropwise addition was one hour. After further aging for one hour, a small amount of the reaction solution was sampled and subjected to infrared spectroscopic analysis. It was found that the absorption at 2270 cm -1 due to the -NCO absorption disappeared. Amount of the reaction solution was 128.9g and the reaction yield was 99%. Whole amount of the reaction product was charged into a separable glass flask and then 4.3g of polyoxyethylene phenyl ether (Emulgen 950), 0.35g of n-dodecyl mercaptane and 357g of water were added thereto, followed by emulsification by a high speed, rotating homomixer (Ultra-talax T25) at 13000 rpm for 5 minutes. Thereafter, the flask was flushed with a nitrogen gas for 30 minutes with stirring. After elevation of the inside temperature to 40°C by heating, 1.3g of M-MAM and 2.6g of 2,2'-azobis(2-amidinopropane) dihydrochloride (V-50) as dissolved in 30g of water were added to the reaction system, followed by polymerization reaction at 70°C for 4 hours, whereby a stable, milky-white aqueous emulsion having a solid concentration of 25 % by weight was obtained. EXAMPLE 12 In Example 11, reaction of 2,4-tolylenediisocyanate with ethyleneglycol monoallyl ether was carried out at first, and then reaction with RfC 2 H 4 OH was carried out. A small amount of the reaction solution was sampled, and the brownish solid residue from removal of the solvent tehrefrom by distillation was determined for melting point, IR absorption and nuclear magnetic resonances. The results are as follows: Melting point: 71-89°C IR absorption: 1700 cm -1 (-NHCOO-) 1100-1300 cm -1 (-CF) 1 H-NMR(CD 3 COCD 3 ) : 19 F-NMR(CD 3 COCD 3 ): Chemical shift(CFCl 3 ∼) F number a -80.19 3 b -125.22 2 c -120.77∼-122.51 11.6 d -112.38 2 (Total 18.6) Then, the reaction product was subjected to emulsion polymerization under the same conditions as in Example 11, whereby a stable, milky-white aqueous emulsion having a solid concentration of 25% by weight was obtained. EXAMPLE 13 22.2g (0.1 mole) of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate and 0.17g of dibutyl tin laurate were charged into a separable glass flask with a stirrer and the flask inside temperature was started to increase, while stirring the mixture. When the inside temperature reached to 50°C. 50.4g (0.1 mole) of fluoroalcohol RfC 2 H 4 OH (average molecular weight: 504; Rf: a perfluoroalkyl group having an average carbon atom number of 8.8) dissolved in 41.4g of MMA and 13.8g of EMA was dropwise added to the mixture solution. while monitoring the inside temperature. When the inside temperature was slowly elevated to 70°C due to the exothermic reaction, rate of dropwise addition was adjusted to keep that temperature. Time required from the start to the end of dropwise addition was one hour. After the dropwise addition, the reaction solution was subjected to aging for 3 hours, and then a small amount of the reaction solution was sampled and subjected to infrared spectroscopic analysis. Absorption due to -NCO absorption was observed at 2270 cm -1 . 10.2g (0.1 mole) of ethyleneglycol monoallyl ether dissolving 0.04g of hydroquinone was slowly dropwise added to the reaction solution so as not to cause vigorous heat generation. Rate of dropwise addition was adjusted to keep the reaction temperature at 70°C. Time for the dropwise addition was one hour. After further aging for one hour, a small amount of the reaction solution was sampled and subjected to infrared spectroscopic analysis and nuclear magnetic resonance determination. It was found that the absorption at 2270 cm -1 due to the -NCO absorption disappeared. Amount of the reaction solution was 136.8g with the reaction yield of 99%. The results of nuclear magnetic resonance determination are given below: 1 H-NMR (CD 3 COCD 3 ) : 19 F-NMR (CD 3 COCD 3 ) : Chemical shift(CFCl 3 ∼) F number a -80.17 3 b -125.21 2 c -120.76 ∼ -122.51 11.6 d -112.38 2 (Total 18.6) Whole amount of the reaction product was charged into a separable glass flask, and then 4.6g of polyoxyethylene phenyl ether (Emulgen 950), 0.35g of n-dodecyl mercaptan and 385g of water were added thereto, followed by emulsification by a high speed, rotating homomixter (Ultra-talax T25) at 13000 rpm for 5 minutes. Thereafter, the flask was flushed with a nitrogen gas for 30 minutes with stirring. After elevation of the inside temperature to 40°C by heating, 1.4g of M-MAM and an aqueous solution containing 2.6g of 2,2'-azobis(2-amidinopropane) dihydrochloride dissolved in 30g of water were added to the reaction system, followed by copolymerization reaction at 70°C for 4 hours, whereby a stable milky-white aqueous emulsion having a solid concentration of 25% by weight was obtained. COMPARATIVE EXAMPLE 1 In Example 1, 130g of 2-hydroxyethyl methacrylate was used in place of ethyleneglycol monoallyl ether, whereby a solution of fluoroalkylated urethane methacrylate in MIBK having a solid concentration of 40% by weight was obtained. A portion of the MIBK solution was sampled and subjected to solvent removal by distillation. The resulting brownish solid residue was determined for melting point and IR absorption. The results of determination are as follows: Melting point: 65-91°C IR absorption: 1700 cm -1 (-NHCOO-) 1100-1300 cm -1 (-CF) 150g of the MIBK solution (60g as fluoroalkylated urethane methacrylate) was charged into a separable glass flask and subjected to copolymerization reaction in the same manner as in Example 6 except that 180.7g of water was used, whereby a milky-white aqueous emulsion having a solid concentration of 20% by weight was obtained. Scums and precipitates were found on the stirring vanes of the flask. COMPARATIVE EXAMPLE 2 17.4g (0.1 mole) of 2,4-tolylenediisocyanate and 0.29g of dibutyl tin dilaurate were charged into a separable glass flask with a stirrer, and the flask inside temperature was started to increase, while stirring the mixture. When the inside temperature reached 50°C, 50.4g (0.1 mole) of fluoroalcohol RfC 2 H 4 OH (average molecular weight: 504; Rf: a perfluoroalkyl group having an average carbon atom number of 8.8) dissolved in 73.2g of MMA and 22g of EMA was dropwise added to the mixture solution, while monitoring the inside temperature. When the inside temperature was slowly elevated to 70° due to the exothermic reaction, rate of dropwise addition was adjusted to keep that temperature. Time required from the start to the end of dropwise addition was one hour. After the dropwise addition, the reaction solution was subjected to aging for 30 minutes, and then a small amount of the reaction solution was sampled and subjected to infrared spectroscopic analysis. Absorption due to -NCO absorption was observed at 2270 cm -1 . Then, 75g (0.1 mole) of CH 2 =CHCH 2 O(C 2 H 4 O) 10 9 [CH(CH 3 )CH 2 O] 38 H (Unisafe PKA-5011, trademark of a product commercially available from NOF Corp., Japan) dissolving 0.07g of hydroquinone was slowly dropwise added to the reaction solution so as not to cause vigorous heat generation. Rate of dropwise addition was adjusted to keep the reaction temperature at 70°C. Time required for the dropwise addition was one hour. Then, the reaction solution was subjected to further aging for one hour, and a small amount of the reaction solution was sampled and subjected to infrared spectroscopic analysis. It was found that the absorption at 2270 cm -1 due to the -NCO absorption disappeared. After removal of MMA and EMA from the sample by distillation, the resulting ocherous, viscous materials were determined for IR absorption. The results are given below: IR absorption: 1700 cm -1 (-NHCOO-) 1100-1300 cm -1 (-CF) The reaction mixture was obtained as 235.8g of a monomer mixture solution (recovery yield: 99%), 99g of which was charged into a separable glass flask. Then, 3.3g of polyoxyethylene phenyl ether (Emulgen 950), 0.25g of n-dodecyl mercaptan and 270g of water were added thereto, followed by emulsification by a high speed rotating homomixer (Ultra-talax T25) at 13000 rpm for 5 minutes. Then, the flask was flushed with a nitrogen gas for 30 minutes with stirring, and after elevation of the inside temperature to 40°C by heating, 1.0g of M-MAM and 2.0g of 2,2'-azobis(2-amidinopropane) dihydrochloride (V-50) dissolved in 30g of water were added to the reaction system, followed by copolymerization reaction at 70°C for 4 hours. With progress of polymerization reaction, precipitates were formed. At the end of polymerization reaction most of the resulting copolymers was settled down as precipitates and no stable aqueous emulsion was obtained. COMPARATIVE EXAMPLE 3 17.4g (0.1 mole) of 2,4-tolylenediisocyanate and 0.18g of dibutyl tin laurate were charged into a separable glass flask with a stirrer, and the flask inside temperature was started to increase while stirring the mixture. When the inside temperature reached to 50°C, 50.4g (0.1 mole) of fluoroalcohol RfC 2 H 4 OH (average molecular weight: 504; Rf: a perfluoroalkyl group having an average carbon atom numbver of 8.8) dissolved in 44g 44g of MMA and 14g of EMA was dropwise added to the mixture solution, while monitoring the inside temperature. After slow elevation of the inside temperature to 70°C due to the exothermic reaction, rate of dropwise addition was adjusted to keep that temperature. Time required from the start to the end of dropwise addition was one hour. After the dropwise addition, the reaction solution was subjected to aging for 30 minutes, and then a small amount of the reaction solution was sampled and subjected to infrared spectroscopic analysis. Absorption due to -NCO absorption was observed at 2270 cm -1 . 20g (0.1 mole) of CH 2 =CHCH 2 O(C 2 H 4 O) 3.2 H (Uniox PKA-5001, trademark of a product commercially available from NOF Corp., Japan) dissolving 0.04g of hydroquinone was slowly dropwise added to the reaction solution so as not to cause vigorous heat generation. Rate of dropwise addition was adjusted to keep the reaction temperature at 70°C. Time required for the dropwise addition was one hour. The reaction solution was subjected to further aging for one hour, and a small amount of the reaction solution was sampled and subjected to infrared spectroscopic analysis. It was found that the absorption at 2270 cm -1 due to the -NCO absorption disappeared. After removal of MMA and EMA from the sample by distillation, the resulting ocherous viscous materials were determined for IR absorption. The results are as follows: IR absorption: 1700 cm -1 (-NHCOO-) 1100-1300 cm -1 (-CF) The reaction solution was obtained as 144.5g of a monomer mixture solution (recovery yield: 99%), 99g of which was subjected to copolymerization reaction in the same manner as in Comparative Example 2, whereby a milky-white aqueous emulsion having a solid concentration of 25% by weight was obtained. COMPARATIVE EXAMPLE 4 Copolymerization reaction was carried out in the same manner as in Comparative Example 2, using 60g of fluoroalkyl acrylate RfC 2 H 4 OCOCH=CH 2 (Rf: a perfluoroalkyl group having an average carbon atom number of 8.8), 30g of MMA and 9g of EMA, whereby a milky-white aqueous emulsion having a solid concentration of 25% by weight was obtained. COMPARATIVE EXAMPLE 5 17.4g (0.1 mole) of 2,4-tolylenediisocyanate and 0.15g of dibutyl tin dilaurate were charged into a separable glass flask with a stirrer, and the flask inside temperature was started to increase, while stirring the mixture. When the inside temperature reached to 50°C, 50.4g (0.1 mole) of fluoroalcohol RfC 2 H 4 OH (average molecular weight: 504; Rf: a perfluoroalkyl group having an average carbon atom number of 8.8) dissolved in 37.8g of MMA and 11.3g of EMA was dropwise added to the mixture solution, while monitoring the inside temperature. After slow elevation of the inside temperature to 70°C due to the exothermic reaction, rate of dropwise addition was adjusted to keep that temperature. Time required from the start to the end of dropwise addition was one hour. After the dropwise addition, the reaction solution was subjected to aging for 30 minutes and a small amount of the reaction solution was sampled and subjected to infrared spectroscopic analysis. Absorption due to -NCO absorption was observed at 2270 cm -1 . 5.8g (0.1 mole) of allyl alcohol dissolving 0.04g of hydroquinone was slowly dropwise added to the reaction solution so as not to cause vigorous heat generation. Rate of dropwise addition was adjusted to keep the reaction temperature at 70°C. Time required for the dropwise addition was one hour. The reaction solution was subjected to further aging for one hour, and a small amount of the reaction solution was sampled and subjected to infrared spectroscopic analysis. It was found that the absorption at 2270 cm -1 due to the -NCO absorption disappeared. After removal of MMA and EMA from the sample by distillation, the resulting brownish solids were determined for melting point and IR absorption. The results are given below: Melting point: 90-96°C IR absorption: 1700 cm -1 (-NHCOO-) 1100-1300 cm -1 (-CF) The reaction solution was obtained as 122.9g of a monomer mixture solution (recovery yield: 99%), 99g of which was subjected to copolymerization reaction in the same manner as in Comparative Example 2, whereby a milky-white, aqueous emulsion having a solid concentration of 21% by weight was obtained. With progress of polymerization reaction, precipitates were started to form. The aqueous emulsions obtained in the foregoing Examples and Comparative Examples were each diluted with water to a solid concentration of 0.5% by weight and sprayed onto polyamide carpets of undyed cut piles by an atomizer to a wet pickup (ratio of the deposited emulsion to the weight of carpet) of 65%. Then, the wet carpets were placed in a hot air-circulating drier and dried at 130°C for 30 minutes. The carpets so treated were tested for the following test items: Water-repellency: Maximum % by weight of isopropanol (IPA) capable of retaining droplets of mixture solutions of isopropanol and water on the carpets at 30 seconds after trickling, when the mixture solutions trickled thereon. Evaluation of water-repellency is made in 11 rankings between 0 and 100, so that evaluation with e.g. an aqueous 30 wt.% IPA solution can have a ranking of 30. Ranking of 0 means complete permeation of water. Water-repellency increases with a higher ranking. Ranking of 100 means no permeation even with 100% IPA. Oil-repellency according to AATCC TM 118-1992: Test solutions having various surface tensions [0: none; 1: Nujol; 2: Nujol-n-hexadecane (65:35) mixture solution; 3: n-hexadecane; 4: n-tetradecane; 5: n-dodecane; 6: n-decane; 7: n-octane; 8: n-heptane] are trickled onto the carpets and evaluation of oil-repellency is made as a maximum value at which droplets of test solutions undergo no permeation even 30 seconds after the trickling. Oil-repellency of 0 means that no droplets of Nujol can be retained at all at 30 seconds after the trickling, that is, the carpets have no oil resistance at all, and oil-repellency of 8 means the highest oil-repellency, for example, droplets of n-heptane can be retained even 30 seconds after the trickling. Anti-dry soiling property according to JIS L-1023-1992: A circular carpet is fixed onto a disc plate on a circular tester and rotated, and a standard soiling material in a composition comprising 40% by weight of peat moss, 17% by weight of portland cement, 17% by weight of kaolin, 17% by weight of diatomaceous earth, 0.1% by weight of carbon black, 0. 15% by weight of iron oxide (III) for ferrite and 8.75% by weight of Nujol is sprayed thereon through two sets of impact rotors, while tapping to soil the carpet. Then, excess standard soiling material is removed therefrom by suction with a vacuum cleaner and lightness is measured by a colorimeter to make evaluation of the anti-dry soiling property. More specifically, 20g of the standard soiling material is filled into the two sets of impact rotors, and to make uniform spraying of the standard soiling material onto the test piece before the main test, a preliminary test piece is fixed onto the disc plate and 100 trial tappings are carried out. Thereafter, the main test is carried out. In the main test, a test piece is fixed on the disc plate and soiled, while making 50 revolutions of the disc plate. Immediately after the soiling, the test piece is vacuum cleaned while making 20 revolutions of the disc plate. Then, one more soiling is carried out, while making 50 revolutions of the disc plate. Immediately after the soiling, the test piece is vacuum cleaned. The foregoing operations are carried out two test pieces. Evaluation of anti-dry soiling property is made by measuring a presoiling lightness L0 * and a postsoiling lightness L1 * each of the two test pieces by a colorimeter (CM-2002, trademark of a meter commercially available from Minolta Camera Co., Ltd, Japan), followed by calculation according to the following calculation equation. An evaluation value is an average degree of soiling of the two carpet test pieces. As the color order system, an L * a * b * color order system set forth by JIS Z-8729-1980 is used. Degree of soiling = L0 * - L1 * L0 * × 100 Emulsion stability: At the end of copolymerization reaction, complete absence of precipitates are marked as O; presence of a small amount of precipitates as Δ; and presence of a very large amount of precipitates as ×. Test results are given in the following Table. Example Water-repellency Oil-repellency Degree of soiling Stability (Untreated) 0 0 28.9 - Example 2 30 3 11.3 ○ " 3 " 3 10.4 ○ " 4 40 4 9.6 ○ " 5 " " 9.4 ○ " 6 " " 8.3 ○ " 7 " " 8.4 ○ " 8 " " 7.9 ○ " 9 " " 10.3 ○ " 10 " " 10.1 ○ " 11 " " 6.8 ○ " 12 " " 8.7 ○ " 13 " " 9.1 ○ Comp. Ex. 1 30 3 20.5 Δ " 3 " " 19.8 ○ " 4 " 2 20.3 Δ " 5 " 3 17.5 × The following is observations of results of Comparative Examples: (1) In Comparative Example 1 as a trace test of JP-B-3-3542, precipitates were formed during the copolymerization reaction, and the water-repellency and the oil-repellency were poorer each by one ranking and the degree of soiling was poorer by 13.7 points than those of Example 11 using reaction product of 2,4-tolylenediisocyate with fluoroalcohol RfC 2 H 4 OH, followed by reaction with ethyleneglycol monoallyl ether. (2) In Comparative Example 3 using reaction product of 2,4-tolylenediisocyanate with fluoroalcohol RfC 2 H 4 OH, followed by reaction with CH 2 =CHCH 2 O(C 2 H 4 O) n H, a stable emulsion could be obtained, but the water-repellency and the oil-repellency were poorer each by one ranking and the degree of soiling was poorer by 13 points than those of Example 11. (3) In Comparative Example 4 using a fluoroalkyl acrylate as a good water-repellent, precipitates were formed during the copolymerization, and the water-repellency was poorer by one ranking, the oil-repellency by two rankings and the degree of soiling by 13.5 points than those of Example 11. (4) In Comparative Example 5 using reaction product of 2,4-tolylenediisocyanate with fluoroalcohol RfC 2 H 4 OH, followed by reaction with allyl alcohol, a large amount of precipitates was formed during the copolymerization, and the water-repellency and the oil-repellency were poorer each by one ranking and the degree of soiling was poorer by 10.7 points than those of Example 11.

Claims: A fluoroalkylated allylurethane represented by the following general formula: RfROCONHR' NHCOOC n H 2n OCH 2 CH=CH 2 where Rf is a perfluoroalkyl group having 2 to 20 carbon atoms, R is a divalent organic group, R' is a diisocyanate residue and n is an integer of 2 to 6. A process for preparing a fluoroalkylated allylurethane represented by the following general formula: RfROCONHR' NHCOOC n H 2n OCH 2 CH=CH 2 where Rf is a perfluoroalkyl group having 2 to 20 carbon atoms, R is a divalent organic group, R' is a diisocyanate residue and n is an integer of 2 to 6, which comprises reacting a diisocyanate compound having two NCO groups of different reactivity in the molecule with a fluoroalcohol represented by the following general formula: RfROH where Rf and R have the same meanings as defined above, followed by reaction with an alkyleneglycol monoallyl ether represented by the following general formula: HOC n H 2n OCH 2 CH=CH 2 where n has the same meaning as defined above. A process according to Claim 2, wherein the diisocyanate compound having two NCO groups of different reactivity in the molecule is 2,4-tolylenediisocyanate, A process according to Claim 2, wherein the diisocyanate compound having two NCO groups of different reactivity is 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate. A process according to Claim 2, wherein the reaction is carried out in an inert organic solvent. A process according to Claim 5, wherein the inert organic solvent is a ketone, an ester or an aromatic hydrocarbon. A process according to Claim 2, wherein the reaction is carried out in a polymerizable monomer. A process according to Claim 7, wherein the polymerizable monomer is a methacrylate ester, an acrylate ester or vinylidene chloride. A process for preparing a fluoroalkylated allylurethane represented by the following general formula: RfROCONHR'NHCOOC n H 2n OCH 2 CH=CH 2 where Rf is a perfluoroalkyl group having 2 to 20 carbon atoms, R is a divalent organic group, R' is a diisocyanate residue and n is an integer of 2 to 6, which comprises reacting a diisocyanate compound having two NCO groups of different reactivity in the molecule with an alkyleneglycol monoallyl ether represented by the following general formula: HOC n H 2n OCH 2 CH=CH 2 where n has the same meaning as defined above, followed by reaction with a fluoroalcohol represented by the following general formula: RfROH where Rf and R have the same meanings as defined above. A process according to Claim 9, wherein the diisocyanate compound having two NCO groups of different reactivity in the molecule is 2,4-tolylenediisocyanate. A process according to Claim 9, wherein the diisocyanate compound having two NCO groups of different reactivity is 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate. A process according to Claim 9, wherein the reaction is carried out in an inert organic solvent. A process according to Claim 12, wherein the organic solvent is a ketone, an ester or an aromatic hydrocarbon. A process according to Claim 9, wherein the reaction is carried out in a polymerizable monomer. A process according to Claim 14, wherein the polymerizable monomer is a methacrylate ester, an acrylate ester or vinylidene chloride. A copolymer obtained by copolymerization of a fluoroalkylated allylurethane represented by the following general formula: RfROCONHR'NHCOOC n H 2n OCH 2 CH=CH 2 where Rf is a perfluoroalkyl group having 2 to 20 carbon atoms, R is a divalent organic group, R' is a diisocyanate residue and n is an integer of 2 to 6, with at least one of a methacrylate ester, an acrylate ester and vinylidene chloride. A copolymer according to Claim 16, wherein the copolymer is obtained by copolymerizing about 30 to about 90% by weight of the fluoroalkylated allylurethane on the basis of total comonomers. A process for preparing an aqueous copolymer emulsion which comprises copolymerizing a fluoroalkylated allylurethane represented by the following general formula: RfROCONHR' NHCOOC n H 2n OCH 2 CH=CH 2 where Rf is a perfluoroalkyl group having 2 to 20 carbon atoms, R is a divalent organic group, R' is a diisocyanate residue and n is an integer of 2 to 6, with at least one of a methacrylate ester, an acrylate ester and vinylidene chloride by emulsion polymerization. A water- and oil-repellent, anti-soiling processing agent, which comprises a copolymer obtained by copolymerization of a fluoroalkylated allylurethane represented by the following general formula: RfROCONHR'NHCOOC n H 2n OCH 2 CH=CH 2 where Rf is a perfluoroalkyl group having 2 to 20 carbon atoms, R is a divalent organic group, R' is a diisocyanate residue and n is an integer of 2 to 6, with at least one of a methacrylate ester, an acrylate ester and vinylidene chloride as an effective component A water- and oil-repellent, anti-soiling processing agent according to Claim 19, which is used in an aqueous emulsion.

Inventors: ISHIDA YUZURU, YAMAMOTO KAZUHIRO, ISHIDA, YUZURU, YAMAMOTO, KAZUHIRO
Applicants: NIPPON MEKTRON KK, NIPPON MEKTRON, LTD.
Application year: 1997
Main classification: D06M15
IPC codes: D06M15, C08G18, D06M13, C07C271, C08F216, C08F16