TW201206972A - Fluorochemical composition for treatment of paper - Google Patents

Abstract

Compound COMP, which is obtainable by reaction of at least two reactants A and B, wherein A is a compound of formula (I); Rf-O-(CF(CF3)CF2O)mCF(CF3)-X-Y-Z (I) with Rf being a perfluorinated alkyl group, m being from 3 to 25; X being a carbonyl group or CH2; Y being a chemical bond or an organic divalent or trivalent linking group bearing a functional or difunctional isocyanate reactive group; Z being an organic group bearing at least one cationic group, and, reactant B is a polyfunctional isocyanate or a mixture thereof, and optionally one or more isocyanate-reactive co-reactants C. The invention also relates to a process for the production of the compound and aqueous dispersions or solutions comprising it and their use for treatment of paper in order to render the paper oil repellent.

Description

201206972 VI. Description of the Invention: [Technical Field] The present invention relates to a fluorine chemical composition obtainable by reacting a polyisocyanate compound with at least one isocyanate-reactive fluorinated polyether compound having at least one cationic group, And the use of paper to prevent oil. [Prior Art] 0 The paper industry produces a wide variety of packaging materials for packaging foods and in contact with food. Paper that comes into contact with oily or fat foods requires anti-fouling and leak-proof barrier properties. Fluorochemicals generally provide such barrier properties by application to the surface of the paper or by addition to the pulp prior to paper formation. An important requirement for treating paper to make it suitable for contact with food is to minimize the risk of contamination of the packaged food by any material that is harmful or potentially harmful to human or animal health. The best condition is when the paper is not containing any harmful substances at all or at least not releasing harmful substances during its use. The Q fluorochemical should impart oleophobic properties to the treated paper. The perfluoroalkyl derivative is usually a mixture of molecules having different chain lengths of 4 to 20 carbon atoms. A disadvantage of this type of chemical is that it is difficult to completely eliminate the undesired, stubborn and bioaccumulative contaminants perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). The hard part is to find fluorochemicals that do not contain PFOA/PFOS, which have the same or similar application performance compared to existing products. Surprisingly, it has been found that isocyanate-reactive fluorochemical polyethers having at least one cationic group, when reacted with polyfunctional isocyanates -5 to 201206972, make fluorochemical compounds free of PFOA/PFOS on paper It shows unexpectedly good performance. SUMMARY OF THE INVENTION The present invention therefore relates to a compound COMP obtainable by the reaction of at least two reactants A and B and optionally one or more isocyanate-reactive co-reactants C, wherein A is a compound of formula (I):

Rr0-(CF(CF3)CF20)mCF(CF3)-X-Y-Z (I)

Rf is a perfluoroalkyl group; m is 3 to 2 5 ; X is a carbonyl group or CH 2 ; Y is a chemically bonded or organic double or triple bond group having a monofunctional or difunctional isocyanate reactive group; At least one organic group of a cationic group, and the reactant B is a polyfunctional isocyanate or a mixture thereof. Preferably, reactant A is a mixture of compounds of formula (I) wherein m is from 4 to 22. Preferably, reactant A has from 750 to 4000 g/mole, more preferably from 100 to 3000 g/mol and even more preferably has an average molecular weight of from 1 5 Å to 2500 g/mole. Preferably, the reactant A additionally contains 0 to 10% by weight, more preferably 5% to 5% by weight, even more preferably 〇 to 1% by weight, particularly preferably 〇 to 1% by weight, having less than 750 g. /Mole molecular weight compound, the weight % based on the total weight of the reactant-6-201206972 A. Preferably, reactant A is a compound of formula (I) wherein X is a carbonyl group. Preferably, reactant A is a compound of formula (I) wherein Y is one or two isocyanate-reactive groups (including mercaptans, hydroxyl groups and amine groups, more preferably amine groups, even more preferably secondary A linking group of an amine group. Preferably, reactant A is a compound of formula (I) wherein Z is a linking group having one cationic group to less than zero, including a tertiary amine, N-oxide or ammonium group. The N-oxide or ammonium group can also be obtained by treatment of a tertiary amine group after the reaction between reactants A and B. More preferably, the reactant A is a compound of (II): Rr0-(CF(CF3)CF20)mCF(CF3)-C0N(R1)-R2-NH-R3-N(R4)2 (II) wherein m As defined above, and all preferred embodiments thereof, R1 is hydrogen or an alkyl group such as 1 to 4 carbon atoms, Q R2 and R3 are independently an alkylene group having 1 to 15 carbon atoms, and R 4 is An alkyl group of 1 to 4 carbon atoms. Preferably, reactant A is a compound of formula (II) wherein Rf and m are as defined above and all preferred embodiments thereof, R1 is hydrogen, R2 and R3 are alkylene groups of 2 or 3 carbon atoms, and R4 is methyl. Preferably, reactant B is a mixture of polyisocyanates having at least 3 isocyanate groups or polyisocyanate compounds having an average of more than 2 isocyanate groups per molecule, such as diisocyanate compounds and having at least 3 isocyanates A mixture of isocyanate compounds. The polyisocyanate 201206972 acid ester can be aliphatic or aromatic. Examples include hexyl diisocyanate, 2,2,4-trimethyl-1,6-extended hexyl diisocyanate, 1,2-extended ethyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1 , 3,6-extended hexyl isocyanate, cyclic trimer of hexyl diisocyanate, cyclic trimer of isophorone diisocyanate, 4,4'-methyldiphenyl diisocyanate, 4, 6-di-(trifluoromethyl)-1,3-benzenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, o-, m- and p-xylene diisocyanate, 4, 4'-diisocyanoquinone diphenyl ether, 3,3-dichloro-4,4'-diisocyanoquinone diphenylmethane, 4,5'-diphenyl diisocyanate, 4,4'-diiso Cyanonylbenzyl, 3,3'-dimethoxy-4,4'-diisocyanide diphenyl, 3,3'-dimethyl-4,4,-diisocyanide diphenyl, 2,2'-Dichloro-5,5'-dimethoxy_4,4'-diisocyanide diphenyl, 1,3-diisocyanoquinone, 1,2-naphthalene diisocyanate, 4 -Chloro-l,2-naphthalene diisocyanate, 1,3-naphthalene diisocyanate, 1,8-dinitro-2,7-naphthalene diisocyanate, polyphenylene polyphenyl isocyanate, 3-isocyanide Methyl-3,5,5-trimethylcyclohexyl isocyanate, polymethylene polyphenylene isocyanate, isocyanate containing self-condensing moiety such as polyisocyanate containing biuret or isocyanurate, or a diisocyanate of a specific diketone (azetedinedione). Preferably, a co-reactant C comprising a non-fluorinated or fluorinated organic compound having one or more isocyanate-reactive groups is used. Preferably, the co-reactant C is a fluorinated organic compound having one or more isocyanate-reactive groups. More preferably, the co-reactant C is a compound of the formula (III) (Rr〇-(CF(CF3)CF2〇)mCF(CF3)-X)n-Q (III) 201206972 wherein

Rf, X and m are as defined above and all preferred embodiments thereof, Q is an organic group having a monofunctional or difunctional isocyanate-reactive group or an organic divalent or trivalent linking group; η is 1 or 2 . Preferably, the co-reactant C is a compound of the formula (III) wherein Q is one or two isocyanate-reactive groups (such as a thiol, a hydroxyl group, and an amine group 'preferably an amine group' or even more preferably The organic group of the secondary amine group. More preferably, the co-reactant C is a compound of formula (IVa) or (IVb) or a mixture of the two:

Rr〇-(CF(CF3)CF20)mCF(CF3)-CON(R1)-R2-OH (IVa) (Rr〇-(CF(CF3)CF20)mCF(CF3)-C〇N(R1)-R2 nN(R5)H (IVb) wherein Rf, R1, R2, m and n are as defined above and all preferred embodiments thereof, R5 is hydrogen (if η is 1) or an alkyl group having 1 to 4 carbon atoms .甚至 Even more preferably, the co-reactant C is a compound of the formula (IVb). Preferably, the total stoichiometry of the isocyanate-reactive groups of reactant A and co-reactant C is less than or equal to the total stoichiometry of the isocyanate groups of reactant B; more preferably, reactant A and co-reaction The total stoichiometry of the isocyanate-reactive group of the substance C is 0.8 to 1 times the total stoichiometric amount of the isocyanate group of the reactant B. In an even more preferred embodiment, the total stoichiometry of the isocyanate-reactive groups of reactant A and co-reactant C is from 0.9 to 1 times the total stoichiometric amount of the isocyanate group of reactant B. Preferably, the total chemistry of the isocyanate-reactive group of the co-reactant C-9 - 201206972 is 0 to times the total stoichiometry of the isocyanate-reactive group of the reactant A, more preferably 〇 to 7 times' Even better is 0 to 4 times 'even better, it is up to 1 time. If the total stoichiometry of the isocyanate-reactive groups of reactant A and co-reactant C is less than the total stoichiometry of the isocyanate groups of reactant B, then the excess isocyanate groups are preferably via self-polymerization or The reaction of the polyfunctional isocyanate-reactive compound (including water, polyol or polyamine) is further polymerized. Further, the subject of the present invention is a method for producing a compound COMP, which is characterized in that reactant B is reacted with reactant A and optionally co-reactant C, and reactants A, B and C have the meanings as described above. All preferred examples. Any order of addition can be used. Preferably, reactant A and co-reactant C are simultaneously added to reactant B. Preferably, the stoichiometry of reactants A, B and C has the same meaning as described above and all preferred embodiments thereof. Preferably, the reaction temperature is 〇 to 120 ° C and more preferably 20 to 8 ° C; more preferably, the pressure is between atmospheric pressure and 2 bar, and more preferably between atmospheric pressure and 1.2 bar. Preferably, the reaction time is from 1 minute to 48 hours, and more preferably from 1 minute to 6 hours. The reaction can be carried out in the presence or absence of a catalyst. Suitable catalyst for the absorption of guanamine; tin salts such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di(2-ethylhexanoate), stannous octoate, stannous oleate, chlorinated -10-201206972 Tin; barium salts and others are known to those skilled in the art. Generally, the preferred concentration of the catalyst is from 0.001% by weight to 1% by weight, based on the total weight of the reactants, and preferably from 0.1% by weight to 5% by weight. Preferably, the reaction is carried out in the absence of any catalyst. In another preferred embodiment, the reaction is carried out in an aprotic solvent or aprotic solvent mixture. Preferred solvents are acetone, ethyl acetate, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, diethyl ether, tert-butyl methyl ether, hydrofluoroether (such as methoxy nonafluorobutane), trifluorotoluene, 1, 3-bis(trifluoromethyl)benzene and mixtures thereof. This reaction can be controlled, for example, by infrared (IR) spectrometry. Unreacted reactant B can be removed by washing COMP with a non-fluorinated organic solvent that does not dissolve COMP. A further subject of the invention is an aqueous dispersion of the compound COMP, DISP or solution SOL. Preferably, the dispersion DISP or solution SOL comprises 0.5 to 40% by weight of the Q compound COMP, more preferably 5 to 30% by weight, based on the total weight of the dispersion D I S P or the solution S Ο L. Therefore, the compound C Ο Μ P is preferably dispersed or dissolved in water. In addition to water, the dispersion or solution may or may not be present as a cosolvent. Preferably, the cosolvent can be slowly added to the reaction mixture' while any solvent used during the preparation of the compound COMP is distilled off' and the resulting product is neutralized with acid and then water is added. Preferably, the distillation of the solvent of the reaction is carried out under vacuum. -11 - 201206972 Preferably, the acid used for neutralization is selected from the group consisting of acetic acid and lactic acid, caproic acid, benzoic acid, caPrilic acid, citric acid, formic acid, sebacic acid, boric acid, and different Phthalic acid, itaconic acid, lauric acid, maleic acid, malic acid, oxalic acid, phosphoric acid, phthalic acid, pyromellitic acid, succinic acid, terephthalic acid, ascorbic acid, hypophosphorous acid, hydroquinone (propionic acid), acid extension, sodium hydrogen sulfate or terephthalic acid, valeric acid, p-hydroxybenzoic acid, resin acid and rosin acid, salicylic acid, sebacic acid. The cosolvent used in the dispersion or solution is preferably water soluble or at least partially water soluble, more preferably the cosolvent has at least one hydroxyl group, and even more preferably the cosolvent is a diol. In a preferred embodiment, the cosolvent is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, hexanediol- Π, 6], hexanediol, polytetrahydrofuran, monoalkyl ethers of these diols, and mixtures of these solvents. Optionally, the compound COMP can be dispersed or dissolved in a cosolvent or a mixture which does not contain water, and the cosolvent is as defined above and all of its specific examples. Preferably, the temperature for the dispersion or for dissolution is 25 to 2 0 0 ° C, more preferably 25 to 150 ° C, still more preferably 25 to 100 ° C. Preferably, the reaction time for dispersion or dissolution is from 5 minutes to 6 hours. Another subject of the invention is that the use of the compound COMP is preferably in the form of a dispersion DISP or solution SOL for treating paper to make paper oil-proof. A further subject of the invention is a method of making paper' which is characterized in that -12-201206972 treats paper with compound COMP. Preferably, the paper is treated with the compound COMP in the form of dispersion DISP or solution SOL. Further, the present invention relates to a paper treated with a solution or dispersion containing the compound COMP. The compound COMP of the present invention can be used for paper sizing by using an application method known in the prior art. For example, it can be applied by surface treatment (gluing and/or coating) the formed paper.另一 Another method is the wet-end method, which is the application method in paper awards. For the application method, paper, paperboard, etc. are dispersed using a suitable medium (water or water and solvent mixture). DISP or solution S Ο L treatment. In the case of surface treatment, the compound COMP can be applied by coating, dipping, coating, or gluing. In a typical application by coating, the amount of compound COMP is from 0.2 to 2% by weight relative to the coating suspension used, and the suspension may contain inorganic tantalum (such as calcium carbonate, kaolin, titanium dioxide). And a binder (for example, a styrene-butadiene copolymer, an acrylic copolymer or a copolymer containing vinyl acetate as a substrate for the pigment). In a typical application of paper sizing by a press, the amount of compound COMP is from 0.2 to 2% by weight relative to the paper system and is used as an aqueous suspension at 20 ° C to 90 ° C. The temperature is fed between the rollers of the upper press device. Other additives (such as starch, functionalized starch, polyvinyl alcohol, carboxymethyl cellulose, melamine resin, urea formaldehyde resin, aldehyde group-containing compound, acrylic resin, styrene-butadiene copolymerization) ()) added to the suspension. Defoamers are usually added to improve the machine's 13-201206972 runnability. Drying can be carried out at a temperature in the range of 90 to 130 ° C according to the general technique used in the paper industry. The dispersion DISP or solution SOL may also contain other products such as known additives required to maintain, modify or modify the properties of the paper, such as those described above. It has been found that an isocyanate-reactive fluorochemical polyether having at least one cationic group, when reacted with a polyfunctional isocyanate, renders a fluorochemical compound free of PFOA/PFOS exhibiting unexpectedly good performance when applied to paper. In addition, the resulting polymer has good thermal stability. [Embodiment] Test method: KIT test

The Kit test is a procedure that characterizes the anti-grease properties of paper. The Kit test involves applying the test solutions Nos. 1 to 16 to the sample while evaluating. Tested according to the test instructions for the Tappi test method for paper and paperboard τ 55 9 . When making a kit solution, the castor oil is weighed because its high viscosity makes the volume measurement less accurate. -14- 201206972

No. Face oil toluene is making a rise] Reward mm 1 96.90/100 0 0 2 87.21/90 5 5 3 77.52/80 10 10 4 67.83 / 70 15 15 5 58.14/60 20 20 6 48.45/50 25 25 7 38.76() 40 30 30 8 29.07/30 35 35 9 19.38/20 40 40 10 9.69/10 45 45 11 0 50 50 12 0 45 55 13 0 35 65 14 0 25 75 15 0 15 85 16 0 0 100 In a good lighting In the smoke cooker, a dark plate was used for the ut test to show the penetration as a darker point. 1) Place each test sample on the surface of the selected clean, dry, test-facing surface. 2) Select the middle numbered Kit test solution and carefully apply a stripe of about 2 cm length to the sample without starting the sample contact dropper and start timing. -15- 201206972 3 ) After 15 seconds, quickly remove excess test solution with clean tissue, apply minimal pressure to the paper surface, and immediately inspect the test area. The failure is indicated by the darkening of the test sample, if a dark background is used; or by a bright spot, if a light box is used. The change in color is due to moisture in the sample as the test solution penetrates into the paper. If the test area is not immediately inspected, evaporation of the volatile components of the test solution will occur and the sample will again obtain its original appearance and be rated as acceptable. 4) If the sample does not pass this first test, select the untested area of the piece and repeat the test using the lower numbered solution. The test was repeated until the highest numbered Kit solution was determined, which was placed on the surface for 15 seconds and did not cause a failure. 5) If the sample passes this first test, repeat the test for the untested area of the sample using the higher numbered Kit solution. The test was repeated until the highest numbered Kit solution was determined, which was placed on the surface for 1 5 seconds without causing a failure. The highest rated kit solution that is qualified is the kit grade of the sample. This test should be performed at least twice. Oil absorption test Use a stretcher to cut a sample of 1 5 cm X 1 5 cm square paper. The test sample is adjusted (2 3 t / 50% relative humidity) and weighed on the balance. 201206972 Record the weight for the oil absorption after the test is completed. Disperse the test oil in the measuring cylinder. This test requires 7 to 8 ml. The oil quickly fell on the surface of the test sample to an approximately spiral/square pattern of 10 cm x 1 cm. Immediately thereafter, '12 cm X 12 cm filter paper was placed on the oil' so that the oil was completely covered. The oil immediately penetrates the filter paper and spreads rapidly so that the entire 12 cm x 12 cm test area is completely in contact with the oil. At the same time, start timing. The test was carried out for 10 minutes. The filter paper is then removed from the test sample, after which the residual oil on the test sample is immediately wiped and then wiped off with absorbent tissue until the sample surface is free of oil. The sample is weighed again after the test and the gravity of the oil is calculated. This is called “corn oil absorption”: Jade is collected Ο

Wl = sample weight before test W2 = sample weight after test s = surface area in contact with oil The resulting corn oil absorption is reported in grams per square meter. Tests can be repeated to determine statistically meaningful results. List of materials used: B1: poly(dihexyl isocyanate), Isocyanurate, 193 g / NC0 B2: poly(diisocyanato), Uretdion, 193 g / NC0 B3: poly (diiso) Cetylhexanoate), Isocyanurate, 195.5 g / NC0 -17- 201206972

El: CF3CF2CF2O(CF(CF3)CF20)nCF(CF3)COOCH3, prepared according to WO/2009/1 1 83 48, Mw 1 947 g/mole, free of Mw having less than 1000 g/mole Oligomer. E2: CF3CF2CF2 〇 (CF(CF3)CF20)nCF(CF3)COOCH3, prepared according to WO/2009/1 1 8348, Mw 1971 g/mole, excluding oligo with Mw less than 1000 g/mole Polymer. E3: CF3CF2CF20(CF(CF3)CF20)nCF(CF3)C00CH3, prepared according to WO/2009/1 1 8348, Mw 1 905 g/mole, without Mw having less than 1 000 g/mole Oligomer. E4: CF3CF2CF20(CF(CF3)CF20)nCF(CF3)C00CH3, prepared according to WO/2009/1 1 8348, Mw 1871 g/mole, excluding oligo with Mw less than 1 000 g/mole Polymer. DMAPAPA : H2NCH2CH2CH2NHCH2CH2CH2N(CH3)2 MAPA : H2NCH2CH2CH2NHCH3 DETA : H2NCH2CH2NHCH2CH2NH2 TBME : Third butyl methyl ether BTFMB : 1,3-bis(trifluoromethyl)benzene MNFB : methoxy nonafluorobutane PRG : propylene glycol A c Ο Η : Preparation of Acidic Acid A 1 19 4.7 g of E1 was mounted in a glass reactor equipped with a thermometer, mechanical stirrer and vacuum distillation apparatus and cooled to -1 CTC. 16.0 g of -18-201206972 DMAPAPA was slowly added with stirring and maintained at a temperature of -10 °C - 〇 °C. The mixture was then stirred overnight. The resulting methanol was removed under vacuum to obtain A1. Preparation of A3 Starting from 40.00 grams of E3 and 3.36 grams of DMAPAPA, A3 was prepared according to the procedure described in the preparation of A1. 〇 Preparation of C 1 From 194.7 grams of ugly 1 and 8.86 grams of 8%? At the beginning of eight, C1 was prepared in accordance with the method described in Preparation of Into. Preparation of C3 Starting from 187.1 g of E4 and 5.17 g of DETA, C3 was prepared according to the method described in the preparation of A1. Preparation of ❹ A1/C1 Mix 1 Starting from 58_41 g of E1, 3.200 g of DMAPAPA and 0.886 g of MAPA, A1/C1 Blend 1 was prepared according to the procedure described in the preparation of A1. Preparation of A2/C2 Mixture 1 Starting from 40.00 grams of E2, 2.32 grams of DMAPAPA and 0.51 grams of MAPA, the A2/C2 mixture 1 was prepared according to the procedure described in the preparation of A1. -19- 201206972 Preparation of A2/C2 Mixture 2 Starting from 40.00 g of E2, 2.05 g of DMAPAPA and MAPA of 0.66, the AhC2 mixture 2 was prepared according to the method described in the preparation of A1. Preparation of COMP1 12.11 g of B1 was mounted in a glass reactor equipped with a thermometer, a mechanical stirrer and a vacuum distillation apparatus and diluted with a solvent mixture consisting of 70 g of TBME and 27 g of BTFMB. A mixture of 83.00 grams of A1 and 40.22 grams of C1 was added with stirring. The mixture was stirred at 25 ° C overnight and then heated at 56-6 5 ° C to remove TBME until the mixture thickened to a COMP1 paste with a BTFMB content of about 20%, which would be used directly from 42.18 grams. Eight 2/(:2 Preparation of the mixture starting at 13?1. Then 5 grams of the resulting COMP1 paste was dried at 40 °C / 50 mbar for 24 hours to obtain COMP1. DSC analysis of COMP1 showed no exotherm up to 250. The preparation of COMP2 was started by 42.18 g of human 2/(: 2 mixture 1 and 4.07 g of 81, and a COMP2 paste having a BTFMB content of about 20% was prepared according to the method described in the preparation of COMP1. The COMP2 paste was used directly. For the preparation of DISP3, about 1 gram of the obtained COMP2 paste was dried at 40 ° C / 50 mbar for 24 hours to obtain COMP 2. The DSC analysis of COMP 2 showed no exotherm up to 25 ° C. Preparation of COMP 3 - 201206972 by 42.0 Starting with A2/C2 mixture 2 and 4.07 g of B1, a COMP3 paste having a BTFMB content of about 20% was prepared according to the method described in the preparation of COMP 1. The COMP3 paste was directly used to prepare DISP4. About 1 gram of the obtained COMP3 The paste is dried at 40 ° C / 50 mbar for 24 hours to obtain DSC analysis of COMP3.COMP3 showed no exotherm up to 250 ° C. Preparation of COMP4 0 Starting from 22.84 g of human 1, 11.26 g (: 1 and 3.34 g of 82, prepared according to the method described in the preparation of COMP 1 with approximately 20 % BTFMB content of COMP4 paste. COMP4 paste will be used directly to prepare DISP5. About 1 gram of the resulting COMP4 paste is dried at 40 ° C / 50 mbar for 24 hours to obtain COMP4. DSC analysis of COMP4 shows no exotherm Up to 250 ° C. Preparation of COMP5 Starting from 42.7 g of A3 and 3.34 g of B3, COMP5 paste with a BTFMB content of about 1 5% was prepared according to the method described in Preparation Q of COMP 1. COMP5 paste was used directly for preparation. DISP6. About 1 gram of the resulting COMP5 paste was dried at 40 ° C / 50 mbar for 24 hours to obtain COMP 5. The DSC analysis of COMP5 showed no exotherm up to 250 ° C. The preparation of COMP6 consisted of 32.25 g of A3, 15 g of C3 and Starting with 4.03 grams of B3, a COMP6 paste having a TBME content of about 25% was prepared according to the method described in the preparation of COMP 1. The COMP6 paste was directly used to prepare DISP6. The resulting COMP5 paste of about 1 gram - 21 - 201206972 Dry at 4 (TC / 50 mbar for 24 hours) Was COMP5. DSC analysis of COMP5 showed no exotherm up to 250 °C. Preparation of DISP1 42.5 grams of COMP1 paste was placed in a glass reactor equipped with a thermometer, mechanical stirrer and vacuum distillation unit. The mixture is heated to 1 〇〇 °C. 0.5 g of AcOH was added with stirring, followed by a slow addition of 51 g of PRG over a period of about 1 hour, while residual BTFMB was removed at 100 ° C / 800-50 mbar. Heating was then stopped and 0.4 g of AcOH was added, followed by dropwise addition of 141 g of distilled water. At the end of the addition of water, the mixture was further cooled to 25 it. Then, 卩11 is adjusted to 4.5 by the person £:011 to obtain 013?1. Preparation of DISP2 61.5 grams of A1/C1 Mix 1 was diluted with 60 grams of MNFB. 6·02 gram of B1 was added under stirring. The mixture was stirred at 25 ° C overnight and then refluxed for 4 hours. 0.9 g of AcOH was added, followed by the slow addition of 92.3 g of PRG over about 1 hour while distilling NFB. Finally, the residual MNFB is removed at 100 ° C / 800-200 mbar. Heating was then stopped and 0.76 grams of AcOH was added, followed by the dropwise addition of 206 grams of distilled water. At the end of the addition of water, the mixture was further cooled to 25 t. Then, the pH was adjusted to 4.5 with AcOH to obtain 018 卩2. Preparation of DISP3 Starting from 56.8 grams of COMP2 paste, DISP3 was prepared according to the method described in the preparation of DISP1, -22-201206972. Preparation of DISP4 DISP4 was prepared according to the procedure described in the preparation of DISP1 starting with 56.8 grams of COMP3 paste. Preparation of DISP5 Starting from 45.8 grams of COMP4 paste, DISP5 was prepared according to the method described in the preparation of DISP1. Preparation of DISP6 DISP6 was prepared according to the method described in the preparation of DISP1 starting with 27.63 grams of COMP5 paste. Starting with 56 grams of COMP5 paste, DISP7 was prepared as described in the preparation of DISP1. 〇 Application Example An aqueous solution of 16% starch TCF 07311 was prepared at 100 °C for 15 minutes and then cooled to 75 °C. The dispersions of 1 g, 2 g, 3 g and 4 g of DISP were diluted to 50 g and 50 g of a 16% starch solution was added to obtain an application liquid. Paper samples (68 g/m2) were processed on a Mathis Typ HFP 56700 press at 3 bar/10 m/min and then dried on a 95 °C Schroeter dryer for 2 minutes. The absorption of the compound C Ο Μ P was calculated based on the wet absorption amount and the DISP concentration. The dried paper is adjusted, then -23-201206972 according to the Kit test described, using the paper and Tappi test methods, according to the Kit test Kit rating. The test results are summarized in the table below. Resistance to grease of plate T5 5 9 According to oil absorption, measurement -24- 201206972

Application example number Average absorption average Kit grade oil absorption (tested DISP number) [g/m2] [g/m2] Application example 1 0.057 4 2 (DISP1) 0.116 7 4 0.170 10 4 0.220 13 2 Application Example 2 0.055 3 2 (DISP2) 0.118 7 6 0.172 11 4 0.226 14 4 Application Example 3 0.071 3 7 (DISP3) 0.134 7 2 0.213 10 3 0.305 13 3 Application Example 4 0.060 4 13 (DISP4) 0.103 5 4 0.158 11 3 0.217 14 3 Application example 5 0.071 3 5 (DISP5) 0.149 8 3 0.213 1114 3 0.272 3 Application example 6 0.057 3 7 (DISP6) 0.114 5 2 0.168 9 1 0.221 10 1 Application example 7 0.056 0 5 (DISP7) 0.114 5 2 0.168 9 1 0.222 11 1 -25-

Claims (1)

201206972 VII. Patent Application Range: 1. A compound COMP which can be obtained by the reaction of at least two reactants A and B and optionally one or more isocyanate-reactive co-reactants C, wherein A is a compound of formula (I): Rf-0-(CF(CF3)CF20)mCF(CF3)-XYZ (I) wherein Rf is a perfluoroalkyl group; m is 3 to 25; X is a carbonyl group or CH2; Y is a chemical bond or has a single function or a double An organic double or triple bond linking group of a functional isocyanate reactive group; Z is an organic group having at least one cationic group, and reactant B is a polyfunctional isocyanate or a mixture thereof. 2. A compound according to claim 1 wherein A is a mixture of compounds of formula (I) wherein m is from 4 to 22. 3. The compound of claim 1 or 2 wherein the reactant A has an average molecular weight in the range of from 750 to 4000 g/mol. 4. A compound according to claim 3, wherein A additionally contains up to 10% by weight of a compound having a molecular weight of less than 75 g/mol, based on the total weight of the reactant A. 5. A compound according to claim 1 or 2, wherein the reactant A is a compound of the formula (I) wherein X is a group. 6. A compound according to claim 1 or 2 wherein A is a compound of formula (I) wherein Y is one or two isocyanate-reactive groups (-26-201206972 comprises a thiol, a hydroxyl group and an amine group, More preferably, it is a linking group of an amine group, and even more preferably a secondary amine group. 7. A compound according to claim 1 or 2 wherein A is a compound of formula (I) wherein Z is a linking group having at least one cationic group including a tertiary amine, an N-oxide or an ammonium group. group. 8. A compound of claim 1 or 2 wherein A is a compound of formula (II): 0 Rr〇-(CF(CF3)CF2〇)mCF(CF3)-CON(R1)-R2-NH-R3 -N(R4)2 (II) wherein R1 is hydrogen or an alkyl group, R2 and R3 are independently an alkylene group having 1 to 15 carbon atoms, and R4 is an alkyl group having 1 to 4 carbon atoms. 9. A compound according to claim 1 or 2 wherein B is a mixture of polyisocyanates having at least 3 isocyanate groups or polyisocyanate compounds having an average of more than 2 isocyanate groups per molecule. A compound according to claim 1 or 2, wherein the co-reactant C is a fluorinated organochemical compound having one or more isocyanate-reactive groups. A compound according to claim 1 or 2, wherein the co-reactant c is a compound of the formula (III) (Rr〇-(CF(CF3)CF20)mCF(CF3)-X)nQ (III) wherein Rf , X and m are as defined in claim 1 and Q is an organic group having a monofunctional or difunctional isocyanate-reactive group or an organic divalent or trivalent linking group; ! is 1 or 2. 12. A compound according to claim 1 or 2 wherein C is a compound of formula (IVa) or (IVb): -27- 201206972 Rr0-(CF(CF3)CF20)mCF(CF3)-C0N(R1) -R2-0H (IVa) (Rr0-(CF(CF3)CF20)mCF(CF3)-C0N(R1)-R2)nN(R5)H (IVb) wherein Rf, R1, R2, m and n are as before Definitions, and R5 is hydrogen or an alkyl group having from 1 to 4 carbon atoms if n=l. The compound of claim 1 or 2 wherein the total stoichiometry of the isocyanate-reactive groups of reactant A and co-reactant C is less than or equal to the total stoichiometry of the isocyanate groups of reactant B. 1 4. The compound of claim 1 or 2, wherein the total stoichiometry of the isocyanate-reactive groups of reactant A and co-reactant C is 0.9 to 1 of the total stoichiometric amount of the isocyanate group of reactant B. Times. A method for producing a compound according to any one of claims 1 to 14 wherein the reactants A, B and optionally C are at a temperature in the range of 0 to 120 ° C and atmospheric pressure. React under pressure of 2 bar. 16. The method of claim 15, wherein the reaction is carried out in the presence of a catalyst, preferably at a concentration of from 0.001% by weight to 1% by weight based on the total weight of the reactants. 17. The method of claim 15, wherein the reaction is carried out in a mixture of an aprotic solvent or an aprotic solvent. An aqueous dispersion or aqueous solution containing a compound according to one or more of the first to fourth aspects of the patent application, wherein the concentration of the compound is from 0.5 to 40% by weight '% by weight of the dispersion Or the total weight of the solution is 190. The aqueous dispersion or aqueous solution of claim i, wherein the compound is dispersed or dissolved in water, optionally in the presence of a cosolvent -28-201206972. 20 0. A use of a solution or dispersion of the application of claim 18 or 19 for treating paper to prevent oil from being tarnished. 2 1 . A paper sheet which is treated with a solution or dispersion as disclosed in claim 18 or 19. 201206972 IV Designated representative: (1) The representative representative of the case is: None (2) The symbol of the symbol of the representative is simple: None 201206972 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None