Treatment comprising water- and oil-repellent agent

Abstract

A textile having high fluorine adhesion rate, and excellent water- and oil-repellency can be obtained by a method of producing a treated textile, comprising steps of: (1) preparing a treatment liquid comprising a water- and oil-repellent agent which comprises at least one fluorine-containing compound selected from the group consisting of a fluorine-containing polymer or a fluorine-containing low molecular weight compound, (2) adjusting pH of the treatment liquid to at most 7, (3) applying the treatment liquid to a textile, (4) treating the textile with steam, and (5) washing the textile with water and dehydrating the textile, wherein the treatment liquid comprises a thermally gelling substance.

Claims

1. A method of producing a treated textile, comprising steps of: (1) preparing a treatment liquid comprising a water- and oil-repellent agent which comprises a fluorine-containing polymer, (2) adjusting pH of the treatment liquid to at most 7, (3) applying the treatment liquid to a textile, (4) treating the textile with steam, and (5) washing the textile with water and dehydrating the textile, wherein the water- and oil-repellent agent or the treatment liquid comprises a thermally gelling substance, or, in the step (3), the thermally gelling substance is used in addition to the treatment liquid and the thermally gelling substance is applied to the textile with contacting the thermally gelling substance with the treatment liquid, the thermally gelling substance is at least one cellulose compound selected from the group consisting of methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and methyl hydroxypropyl cellulose, the fluorine-containing polymer comprises: (I) a repeating unit derived from a monomer having a fluoroalkyl group, and (II) a repeating unit derived from a fluorine-free monomer, and/or (III) a repeating unit derived from a crosslinkable monomer, and the fluoroalkyl group-containing monomer is of the formula: ##STR00017## wherein X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, a iodine atom, CFX.sup.1X.sup.2 group (in which X.sup.1 and X.sup.2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 10 carbon atoms, a SO.sub.2N(R.sup.1)CH.sub.2CH.sub.2 group (in which R.sup.1 is an alkyl group having 1 to 4 carbon atoms) or a CH.sub.2CH(OY.sup.1)CH.sub.2 group (in which Y.sup.1 is a hydrogen atom or an acetyl group), and Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, and wherein the fluorine-containing polymer is free from an oxyalkylene group; and wherein the amount of the repeating unit (II) is from 0 to 200 parts by weight, and the amount of the repeating unit (III) is from 0 to 30 parts by weight, based on 100 parts by weight of the repeating unit (I), and the amount of the thermally gelling substance is from 0.1 to 100 parts by weight, based on 100 parts by weight of the fluorine-containing polymer.

2. The method according to claim 1, wherein the thermally gelling substance is a material which gels in the presence of water at the temperature of at least 30 C.

3. The method according to claim 1, wherein the thermally gelling substance is insoluble in water at the temperature of at least 30 C.

4. The method according to claim 1, wherein the thermally gelling substance is at least one material selected from the group consisting of methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose.

5. The method according to claim 1, wherein, in the fluoroalkyl group-containing monomer (I), Y is an aliphatic group having 1 to 10 carbon atoms.

6. The method according to claim 1, wherein the fluorine-free monomer (II) is at least one selected from the group consisting of ethylene, vinyl acetate, vinyl halide, vinylidene halide, acrylonitrile, styrene, polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, vinyl alkyl ether, isoprene and a (meth)acrylate ester having an alkyl group.

7. The method according to claim 1, wherein the crosslinkable monomer (III) is at least one selected from the group consisting of diacetoneacrylamide, (meth)acrylamide, N-methylol-acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylamino-ethyl (meth)acrylate, butadiene, chloroprene and glycidyl (meth)acrylate.

8. The method according to claim 1, wherein the fluorine-containing polymer consists essentially of the repeating units (I) and, (II) and/or (III).

9. The method according to claim 1, wherein, in the fluoroalkyl group-containing monomer (I), the carbon number of the Rf group is from 1 to 6.

10. The method according to claim 1, wherein the fluorine-containing polymer consists of (I) the repeating unit derived from a monomer having a fluoroalkyl group and one or both of (II) the repeating unit derived from a fluorine-free monomer and (III) the repeating unit derived from a crosslinkable monomer.

11. The method according to claim 1, wherein the fluorine-free monomer (II) is at least one selected from the group consisting of vinyl halide and vinylidene halide, and the amount of the repeating unit (II) is 0.5 to 80 parts by weight, based on 100 parts by weight of the repeating unit (I).

12. The method according to claim 1, wherein the fluorine-free monomer (II) is vinyl chloride.

13. A textile obtained by the method according to claim 1.

14. The textile according to claim 13, which is a carpet.

15. The textile according to claim 14, wherein the carpet comprises nylon fibers, polypropylene fibers and/or polyester fibers.

16. A treatment liquid for use in a method of treating a textile, comprising: (i) a water- and oil-repellent agent which comprises a fluorine-containing polymer, and (ii) a thermally gelling substance, wherein the method comprises steps of: (1) preparing the treatment liquid comprising the water- and oil-repellent, (2) adjusting pH of the treatment liquid to at most 7, (3) applying the treatment liquid to a textile, (4) treating the textile with steam, and (5) washing the textile with water and dehydrating the textile, wherein the thermally gelling substance is at least one cellulose compound selected from the group consisting of methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and methyl hydroxypropyl cellulose, the fluorine-containing polymer comprises: (I) a repeating unit derived from a monomer having a fluoroalkyl group, and (II) a repeating unit derived from a fluorine-free monomer, and/or (III) a repeating unit derived from a crosslinkable monomer, and the fluoroalkyl group-containing monomer is of the formula: ##STR00018## wherein X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, a iodine atom, CFX.sup.1X.sup.2 group (in which X.sup.1 and X.sup.2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 10 carbon atoms, a SO.sub.2N(R.sup.1)CH.sub.2CH.sub.2 group (in which R.sup.1 is an alkyl group having 1 to 4 carbon atoms) or a CH.sub.2CH(OY.sup.1)CH.sub.2 group (in which Y.sup.1 is a hydrogen atom or an acetyl group), and Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, wherein the fluorine-containing polymer is free from an oxyalkylene group; and wherein the amount of the repeating unit (II) is from 0 to 200 parts by weight, and the amount of the repeating unit (III) is from 0 to 30 parts by weight, based on 100 parts by weight of the repeating unit (I), and the amount of the thermally gelling substance is from 0.1 to 100 parts by weight, based on 100 parts by weight of the fluorine-containing polymer.

17. The treatment liquid according to claim 16, wherein the thermally gelling substance is added to a polymerizable monomer before the polymerization of the fluorine-containing polymer, whereby the water- and oil-repellent agent is prepared.

18. The treatment liquid according to claim 16, wherein after the fluorine-containing polymer is polymerized, the water- and oil-repellent agent is prepared by adding the thermally gelling substance to the fluorine-containing polymer.

19. The treatment liquid according to claim 16, wherein the thermally gelling substance is added to the water- and oil repellent agent to prepare the treatment liquid.

20. The treatment liquid according to claim 16, wherein, in the fluoroalkyl group-containing monomer (I), Y is an aliphatic group having 1 to 10 carbon atoms.

21. The treatment liquid according to claim 16, wherein the fluorine-free monomer (II) is at least one selected from the group consisting of ethylene, vinyl acetate, vinyl halide, vinylidene halide, acrylonitrile, styrene, polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, vinyl alkyl ether, isoprene and a (meth)acrylate ester having an alkyl group.

22. The treatment liquid according to claim 16, wherein the crosslinkable monomer (III) is at least one selected from the group consisting of diacetoneacrylamide, (meth)acrylamide, N-methylol-acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylamino-ethyl (meth)acrylate, butadiene, chloroprene and glycidyl (meth)acrylate.

23. The treatment liquid according to claim 16, wherein the fluorine-containing polymer consists essentially of the repeating units (I) and, (II) and/or (III).

24. The treatment liquid according to claim 16, wherein, in the fluoroalkyl group-containing monomer (I), the carbon number of the Rf group is from 1 to 6.

25. The treatment liquid according to claim 16, wherein the fluorine-containing polymer consists of (I) the repeating unit derived from a monomer having a fluoroalkyl group and one or both of (II) the repeating unit derived from a fluorine-free monomer and (III) the repeating unit derived from a crosslinkable monomer.

26. The treatment liquid according to claim 16, wherein the fluorine-free monomer (II) is at least one selected from the group consisting of vinyl halide and vinylidene halide, and the amount of the repeating unit (II) is 0.5 to 80 parts by weight, based on 100 parts by weight of the repeating unit (I).

27. The treatment liquid according to claim 16, wherein the fluorine-free monomer (II) is vinyl chloride.

Description

PREFERRED EMBODIMENTS OF THE INVENTION

(1) The following Examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof. In the Examples, % is % by weight unless specified otherwise.

(2) Test procedures of the fluorine adhesion rate, the water-repellency and the oil-repellency are as follows.

(3) Fluorine Adhesion Rate

(4) A combustion flask is sufficiently washed with pure water. Then, 15 mL of pure water is charged into the combustion flask, and the weight of the flask containing water is measured. The weight of pure waster is determined by deducting a previously measured weight of the combustion flask from the weight of flask containing water. A platinum basket is heated twice or thrice to fully evaporate water. 75 mg of a carpet pile is weighed on a KIMWIPE, which is folded with enclosing a combustion aid (30 mg) and is positioned in the platinum basket. Oxygen is blown into the combustion flask, and the piles are burned and decomposed, and absorbed into pure water contained in the flask. After the absorption for 30 minutes, 10 mL of an absorption liquid and 10 mL of a buffer liquid (50 mL of acetic acid, 50 g of sodium chloride, 0.5 g of trisodium citrate dihydrate, and 32 g of sodium hydroxide are added to water to give a total amount of 1 L) are charged into a plastic cup and an F ion is measured by an F ion meter with sufficiently stirring. A fluorine adhesion amount and a fluorine adhesion rate are calculated according to the following equations.
Fluorine adhesion amount [ppm]=(Measurement value [ppm]Blank measurement value [ppm])(Pure water weight [g]/Pile weight [mg])1000
Fluorine adhesion rate (%)=(Fluorine adhesion amount after steam treatment, water wash, centrifugal dehydration and thermal curing treatment [ppm])/(Fluorine adhesion amount immediately after squeezed so that WPU (wet pick up) is 400% or 300% [ppm])

(5) The fluorine adhesion rate is shown as Exhaust-ability in the following Tables.

(6) Water-Repellency

(7) A carpet treated with a water- and oil-repellent agent is stored in a thermo-hygrostat having a temperature of 21 C. and a humidity of 65% for at least 4 hours. A test liquid (isopropyl alcohol (IPA), water, and a mixture thereof, as shown in Table I) which has been also stored at 21 C. is used. The test is conducted in an air-conditioned room having a temperature of 21 C. and a humidity of 65%. Droplets of the test liquid in an amount of 50 L (5 droplets) are softly dropped by a micropipette on the carpet. If 4 or 5 droplets remain on the carpet after standing for 10 seconds, the test liquid passes the test. The water-repellency is expressed by a point corresponding to a maximum content of isopropyl alcohol (% by volume) in the test liquid which passes the test. The water-repellency is evaluated as sixteen levels which are Fail, 0, 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 9 and 10 in order of a bad level to an excellent level.

(8) TABLE-US-00001 TABLE I Water-repellency test liquid (% by volume) Isopropyl Point alcohol Water 10 100 0 9 90 10 8 80 20 7 70 30 6 60 40 5 50 50 4 40 60 3 30 70 2.5 25 75 2 20 80 1.5 15 85 1 10 90 0.5 5 95 0.2 2 98 0 0 100 Fail Inferior to isopropyl alcohol 0/water 100
Oil-Repellency

(9) A carpet treated with a water- and oil-repellent agent is stored in a thermo-hygrostat having a temperature of 21 C. and a humidity of 65% for at least 4 hours. A test liquid (shown in Table II) which has been also stored at 21 C. is used. The test is conducted in an air-conditioned room having a temperature of 21 C. and a humidity of 65%. Droplets of the test liquid in an amount of 50 L (5 droplets) are softly dropped by a micropipette on the carpet. If 4 or 5 droplets remain on the carpet after standing for 30 seconds, the test liquid passes the test. The oil-repellency is expressed by a maximum point of the test liquid which passes the test. The oil-repellency is evaluated as nine levels which are Fail, 1, 2, 3, 4, 5, 6, 7 and 8 in order of a bad level to an excellent level.

(10) TABLE-US-00002 TABLE II Oil-repellency test Surface tension Point Test liquid (dyne/cm, 25 C.) 8 n-Heptane 20.0 7 n-Octane 21.8 6 n-Decane 23.5 5 n-Dodecane 25.0 4 n-Tetradecane 26.7 3 n-Hexadecane 27.3 2 Mixture liquid of 29.6 n-Hexadecane 35/nujol 65 1 Nujol 31.2 Fail Inferior to 1

Preparative Example 1

(11) CF.sub.3CF.sub.2(CF.sub.2CF.sub.2).sub.nCH.sub.2CH.sub.2COOCHCH.sub.2 (a mixture of compounds wherein n is 3, 4 and 5, the average of n is 3.1) (40 g), stearyl acrylate (10 g), 2-ethylhexyl methacrylate (10 g), glycidyl methacrylate (2 g), N-methylol acrylamide (2 g), 3-chloro-2-hydroxypropyl methacrylate (1 g), n-lauryl mercaptan (0.1 g), sorbitan monolaurate (2 g), (C.sub.12-C.sub.14)polyoxyethylene(20)alkyl ether (2 g), (C.sub.16-C.sub.18)alkyltrimethyl ammonium chloride (0.5 g), dialkyl (beef tallow)dimethyl ammonium chloride (0.5 g), dipolyoxyethylene benzyl octadecyl ammonium salt (1.5 g), tripropylene glycol (20 g) and ion exchanged water (95 g) were mixed to prepare a mixture liquid. This mixture liquid was heated to 60 C. and then homogenized by a high pressure homogenizer. The resultant emulsified liquid was charged into a 300 mL flask, the atmosphere of the flask was replaced with nitrogen to remove the dissolved oxygen. Then 2,2-azobis(2-amidinopropane) dihydrochloride (0.5 g) was charged. The copolymerization was performed at 60 C. for 3 hours with stirring to give a copolymer emulsion. The copolymer emulsion was diluted with ion exchanged water to prepare a fluorine-containing acrylate-based water- and oil-repellent agent (that is, an aqueous composition) having a solid content of 30% by weight. The composition of the resultant polymer was almost the same as the composition of the charged monomers.

Preparative Example 2

(12) CF.sub.3CF.sub.2(CF.sub.2CF.sub.2).sub.nCH.sub.2CH.sub.2COOCHCH.sub.2 (a mixture of compounds wherein n is 3, 4 and 5, the average of n is 3.1) (40 g), stearyl acrylate (10 g), 2-ethylhexyl methacrylate (10 g), glycidyl methacrylate (2 g), N-methylol acrylamide (2 g), 3-chloro-2-hydroxypropyl methacrylate (1 g), n-lauryl mercaptan (0.1 g), sorbitan monolaurate (2 g), (C.sub.12-C.sub.14)polyoxyethylene(20)alkyl ether (2 g), (C.sub.16-C.sub.18)alkyltrimethyl ammonium chloride (0.5 g), dialkyl (beef tallow)dimethyl ammonium chloride (0.5 g), dipolyoxyethylene benzyl octadecyl ammonium salt (1.5 g), tripropylene glycol (20 g), ion exchanged water (95 g) and hydroxypropyl methyl cellulose (Hydroxypropyl methyl cellulose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) (8 g) were mixed to prepare a mixture liquid. This mixture liquid was heated to 60 C. and then homogenized by a high pressure homogenizer. The resultant emulsified liquid was charged into a 300 mL flask, the atmosphere of the flask was replaced with nitrogen to remove the dissolved oxygen. Then 2,2-azobis[2-(2-imidazolin-2-yl)propane) dihydrochloride (1.0 g) was charged. The copolymerization was performed at 50 C. for 3 hours with stirring to give a copolymer emulsion. The copolymer emulsion was diluted with ion exchanged water to prepare a fluorine-containing acrylate-based water- and oil-repellent agent (that is, an aqueous composition) having a solid content of 30% by weight. The composition of the resultant polymer was almost the same as the composition of the charged monomers.

Preparative Example 3

(13) CF.sub.3CF.sub.2(CF.sub.2CF.sub.2).sub.nCH.sub.2CH.sub.2COOCHCH.sub.2 (a mixture of compounds wherein n is 3, 4 and 5, the average of n is 3.1) (40 g), stearyl acrylate (10 g), 2-ethylhexyl methacrylate (10 g), glycidyl methacrylate (2 g), N-methylol acrylamide (2 g), 3-chloro-2-hydroxypropyl methacrylate (1 g), n-lauryl mercaptan (0.1 g), sorbitan monolaurate (2 g), (C.sub.12-C.sub.14)polyoxyethylene(20)alkyl ether (2 g), (C.sub.16-C.sub.18)alkyltrimethyl ammonium chloride (0.5 g), dialkyl (beef tallow)dimethyl ammonium chloride (0.5 g), dipolyoxyethylene benzyl octadecyl ammonium salt (1.5 g), tripropylene glycol (20 g) and ion exchanged water (95 g) were mixed to prepare a mixture liquid. This mixture liquid was heated to 60 C. and then homogenized by a high pressure homogenizer. The resultant emulsified liquid was charged into a 300 mL flask, the atmosphere of the flask was replaced with nitrogen to remove the dissolved oxygen. Then 2,2-azobis(2-amidinopropane) dihydrochloride (0.5 g) was charged. The copolymerization was performed at 60 C. for 3 hours with stirring to give a copolymer emulsion. The copolymer emulsion was diluted with ion exchanged water to prepare a fluorine-containing acrylate-based water- and oil-repellent agent (that is, an aqueous composition) having a solid content of 30% by weight. Hydroxypropyl methyl cellulose (Hydroxypropyl methyl cellulose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) (8 g) was added to the resultant composition.

Example 1

(14) The fluorine-containing acrylate-based water- and oil-repellent agent (0.13 g) prepared in Preparative Example 1, a 1 wt % aqueous solution of methyl cellulose (Methyl cellulose SM-15, manufactured by Shin-Etsu Chemical Co., Ltd.) (0.5 g) and water (99.73 g) were mixed to prepare a mixture liquid and a 10% aqueous solution of sulfamic acid was added so that the mixture had pH of at most 2 to give a treatment liquid.

(15) A carpet which was washed with water and dehydrated to WPU of 25% (WPU: wet pick up; when 100 g of the carpet absorbs 25 g of a liquid, WPU is 25%) was immersed in the above-mentioned treatment liquid for 30 seconds so that WPU was 250%. Then, an atmospheric pressure steam treatment (temperature: 100 C. to 107 C.) was conducted for 60 seconds under the state that a pile surface was upward. The carpet was lightly rinsed with 2 L of water and then centrifugal dehydration was conducted to give a WPU amount of 25%. Finally, the carpet was thermally treated at 110 C. for 10 minutes. The carpet was three types of polyester (15 cm5 cm, cut pile, density of 44 oz/yd.sup.2), nylon-6 (15 cm5 cm, cut pile, density of 32 oz/yd.sup.2) and polypropylene (15 cm5 cm, cut pile, density of 38 oz/yd.sup.2).

(16) The resultant carpets were subjected to a fluorine adhesion rate measurement, a water-repellency test and an oil-repellency test. The results are shown in Tables 1, 2 and 3.

Example 2

(17) The carpet was treated in the same manner as in Example 1 except that the amount of the fluorine-containing acrylate-based water- and oil-repellent agent prepared in Preparative Example 1 was changed to 0.13 g, and 0.5 g of a 1% aqueous solution of hydroxypropyl methyl cellulose (Hydroxypropyl methyl cellulose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of methyl cellulose.

(18) The resultant carpets were subjected to a fluorine adhesion rate measurement, a water-repellency test and an oil-repellency test. The results are shown in Tables 1, 2 and 3.

Example 3

(19) The carpet was treated in the same manner as in Example 1 except that the amount of the fluorine-containing acrylate-based water- and oil-repellent agent prepared in Preparative Example 1 was changed to 0.13 g, and 0.5 g of a 1 wt % aqueous solution of hydroxyethyl methyl cellulose (Hydroxyethyl methyl cellulose SEB-04T, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of methyl cellulose.

(20) The resultant carpets were subjected to a fluorine adhesion rate measurement, a water-repellency test and an oil-repellency test. The results are shown in Tables 1, 2 and 3.

Example 4

(21) The fluorine-containing acrylate-based water- and oil-repellent agent (0.13 g) prepared in Preparative Example 2 and water (99.73 g) were mixed to prepare a mixture liquid and a 10% aqueous solution of sulfamic acid was added so that the mixture had pH of at most 2 to give a treatment liquid.

(22) A carpet (15 cm5 cm, nylon-6, cut pile, density of 32 oz/yd.sup.2) which was washed with water and dehydrated to WPU of 25% (WPU: wet pick up; when 100 g of the carpet absorbs 25 g of a liquid, WPU is 25%) was immersed in the above-mentioned treatment liquid for 30 seconds so that WPU was 250%. Then, an atmospheric pressure steam treatment (temperature: 100 C. to 107 C.) was conducted for 60 seconds under the state that a pile surface was upward. The carpet was lightly rinsed with 2 L of water and then centrifugal dehydration was conducted to give a WPU amount of 25%. Finally, the carpet was thermally treated at 110 C. for 10 minutes.

(23) The resultant carpet was subjected to a fluorine adhesion rate measurement, a water-repellency test and an oil-repellency test. The results are shown in Table 1.

Example 5

(24) The carpet was treated in the same manner as in Example 4 except that the fluorine-containing acrylate-based water- and oil-repellent agent prepared in Preparative Example 3 was used.

(25) The resultant carpet was subjected to a fluorine adhesion rate measurement, a water-repellency test and an oil-repellency test. The results are shown in Table 1.

Comparative Example 1

(26) The carpet was treated in the same manner as in Example 1 except that the solution of methyl cellulose was not added to 0.13 g of the fluorine-containing acrylate-based water- and oil-repellent agent prepared in Preparative Example 1.

(27) The resultant carpets were subjected to a fluorine adhesion rate measurement, a water-repellency test and an oil-repellency test. The results are shown in Tables 1, 2 and 3.

(28) TABLE-US-00003 TABLE 1 Polyester Exhaustability (adhesion Water Oil rate) (%) repellency repellency Example 1 82 9 5 Example 2 87 8 4 Example 3 92 10 6 Example 4 85 10 6 Example 5 97 8 4 Comparative 42 3 2 Example 1

(29) TABLE-US-00004 TABLE 2 Nylon Exhaustability (adhesion Water Oil rate) (%) repellency repellency Example 1 80 7 4 Example 2 85 6 5 Example 3 89 8 4 Comparative 41 2 1 Example 1

(30) TABLE-US-00005 TABLE 3 Polypropylene Exhaustability (adhesion Water Oil rate) (%) repellency repellency Example 1 80 4 3 Example 2 87 6 4 Example 3 82 5 4 Comparative 35 2 1 Example 1