WATER-REPELLENT COMPOSITION

Abstract

A water-repellent composition containing (1) a polymer having 2-100 wt %, with respect to the polymer, of a repeating unit derived from an amide group-containing monomer (a) represented by the following formula

##STR00001##

[wherein R.sup.1 is an organic moiety having an ethylenically unsaturated polymerizable group, R.sup.2 is a C.sub.7-30 hydrocarbon group, and R.sup.3 is a C.sub.1-5 hydrocarbon group], (2) a co-agent containing at least one co-agent compound selected from the group consisting of a blocked isocyanate compound, a melamine resin, a silicone polymer, a wax, an acetylene-based emulsifier, and a polyoxyalkylene group-containing emulsifier, and (3) a liquid media. Preferably, the water-repellent composition includes no fluoroalkyl group-containing monomer, and preferably no fluorine-containing monomer. Also disclosed is a method for producing the water-repellent composition, a method for treating a substrate with the water-repellent composition, and a method for producing a treated textile product which includes treating a textile product with the water-repellent composition.

Claims

1. A water-repellent composition comprising: (1) a polymer having 2 to 100% by weight, based on the amount of the polymer, of a repeating unit derived from (a) an amide group-containing monomer represented by the formula: ##STR00008## wherein R.sup.1 is an organic residue having an ethylenically unsaturated polymerizable group, R.sup.2 is a hydrocarbon group having 7 to 30 carbon atoms, and R.sup.3 is a hydrocarbon group having 1 to 5 carbon atoms; (2) a combination agent comprising at least one combination compound selected from the group consisting of a blocked isocyanate compound, a melamine resin, a silicone polymer, a wax, an acetylene-based emulsifier, and a polyoxyalkylene group-containing emulsifier; and (3) a liquid medium.

2. The water-repellent composition according to claim 1, wherein, in the monomer (a), R.sup.1 is —C(═O)CR.sup.11═CH.sup.2, wherein R.sup.11 is a hydrogen atom or a methyl group.

3. The water-repellent composition according to claim 1, wherein the polymer (1) further has a repeating unit derived from a polymerizable monomer other than the monomer (a), and the polymerizable monomer other than the monomer (a) is a compound represented by the formula:
CH.sub.2═CA-T wherein A is a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, or an iodine atom, and T is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a chained or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a chained or cyclic organic group having an ester bond and having 2 to 41 carbon atoms.

4. The water-repellent composition according to claim 3, wherein the polymerizable monomer other than the monomer (a) is at least one selected from the group consisting of: (b) an acrylate ester monomer; (c) a fluorine-free crosslinkable monomer; and (d) a halogenated olefin monomer.

5. The water-repellent composition according to claim 4, wherein the acrylate ester monomer (b) is at least one selected from the group consisting of: (b1) an acrylate ester monomer having an aliphatic hydrocarbon group; and (b2) an acrylate ester monomer having a cyclic hydrocarbon group, the fluorine-free crosslinkable monomer (c) is a compound having at least two ethylenically unsaturated double bonds or a compound having at least one ethylenically unsaturated double bond and at least one reactive group, and the halogenated olefin monomer (d) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.

6. The water-repellent composition according to claim 4, wherein in the polymer, the amount of the repeating unit (b) is 0 to 200 parts by weight, the amount of the repeating unit (c) is 0 to 50 parts by weight, and the amount of the repeating unit (d) is 0 to 100 parts by weight, based on 100 parts by weight of the repeating unit (a).

7. The water-repellent composition according to claim 1, wherein in the combination agent (2), the blocked isocyanate compound is a compound having an isocyanate group moiety (a blocked isocyanate group) in which at least one isocyanate group is blocked with a blocking agent and having no polymerizable unsaturated group, the melamine resin is a polycondensate of melamine and aldehyde, the silicone polymer is a polymer represented by the formula:
(R.sup.23).sub.3Si—O—[—Si(R.sup.21).sub.2—O—].sub.a—[—Si(R.sup.21)(R.sup.22)—O—].sub.b—Si(R.sup.23).sub.3 wherein each R.sup.21 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, each R.sup.22 independently represents a saturated hydrocarbon group having 23 to 40 carbon atoms, each R.sup.23 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a saturated hydrocarbon group having 23 to 40 carbon atoms, a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 5 to 200, in the wax, a compound constituting the wax has 20 to 60 carbon atoms, the acetylene-based emulsifier is an alcohol having unsaturated triple bond or an alkylene oxide adduct of this alcohol, and the polyoxyalkylene group-containing emulsifier is a nonionic surfactant in which an alkylene group in an oxyalkylene group has 2 to 10 carbon atoms, and a molecule of the polyoxyalkylene group-containing emulsifier has 2 to 100 oxyalkylene groups.

8. The water-repellent composition according to claim 7, wherein the blocked isocyanate compound is a reaction product of an isocyanate represented by A(NCO).sub.m, wherein A is a group remaining after isocyanate groups are removed from a polyisocyanate, and m is an integer of 2 to 8, and a blocking agent represented by RH, wherein R is optionally a hydrocarbon group optionally substituted by a hetero atom such as a nitrogen atom or an oxygen atom, and H is a hydrogen atom, the melamine resin is a partially or fully methylolated melamine resin obtained by a reaction between melamine and an aldehyde, the silicone polymer is a compound represented by the formula: ##STR00009## wherein a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is 5 to 200, and n is an integer of 19 to 36, the wax is constituted by at least one compound selected from the group consisting of a normal alkane having 20 to 60 carbon atoms and a normal alkene having 20 to 60 carbon atoms, in the acetylene-based emulsifier, an acetylene alcohol compound is a compound represented by the formula:
HO—CR.sup.31R.sup.32—C≡C—CR.sup.33R.sup.34—OH, or
HO—CR.sup.35R.sup.36—C≡C—H wherein R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35, and R.sup.36 are each independently the same or different, and are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and the polyoxyalkylene group-containing emulsifier is a condensation product of ethylene oxide and hexyl phenol, isooctyl phenol, hexadecanol, oleic acid, an alkane (C.sub.12-C.sub.16) thiol, a sorbitan monofatty acid (C.sub.7-C.sub.19), or an alkyl (C.sub.12-C.sub.18) amine.

9. The water-repellent composition according to claim 1, wherein the liquid medium (3) is water, an organic solvent, or a mixture of water and an organic solvent.

10. The water-repellent composition according to claim 1, being an external treatment agent or an internal treatment agent.

11. A method for producing the water-repellent composition according to claim 1, comprising mixing a polymer mixture which comprises the polymer (1) and the liquid medium (3) with the combination agent (2) comprising a combination compound.

12. A method for treating a substrate, comprising treating a substrate with the water-repellent composition according to claim 1.

13. A method for producing a treated textile product, comprising treating a textile product with the water-repellent composition according to claim 1.

Description

EXAMPLES

[0377] Hereinafter, the present disclosure will be described in more detail with reference to Examples, but the present disclosure is not limited to these Examples.

[0378] Hereinafter, a part or % or a ratio represents a part by weight, % by weight, or a weight ratio, respectively, unless otherwise specified.

[0379] Test procedures are as follows.

Water-Repellency Test

[0380] A treatment liquid having a solid concentration of 1.5% was prepared, and a test fabric prepared by dipping a piece of fabric in the test solution, then putting the fabric through a mangle, and the heat-treating fabric was used to evaluate its water-repellency. The water-repellency of the treated fabric was evaluated, based on the spray method according to JIS-L-1092 (AATCC-22). The result is denoted by the water-repellency No. as shown in the following table. A higher score indicates better water-repellency.

TABLE-US-00001 Water-repellency No. State 100 No wetting or water droplets adhesion on surface 90 No wetting but small water droplets adhesion on surface 80 Wetting on separate small water droplets on surface 70 Wet on half of surface and separate small wet which penetrates fabric 50 Wet on whole surface 0 Wet on whole of front and back surfaces

Water-Repellent Washing Durability

[0381] Washing was repeated 20 times in accordance with JIS L-0217103, and the water-repellency thereafter was evaluated (HL20).

Gum-Up Property

[0382] A polymer dispersion is prepared with water having a hardness of 16 such that the solid concentration reaches 1.8% to prepare 1,000 g of a diluted liquid. The liquid is placed in a pad of which the temperature can be controlled to 40° C. A polyester fabric having a width of 20 cm and a length of 80 cm and formed in a loop for continuous treatment is continuously treated through a mangle at a mangle pressure of 0.4 MPa for 1 hour. After 1 hour, the amount of solids attached to the mangle was observed visually and by touching with a hand to evaluate the gum-up property.

[0383] Good: No solid is attached

[0384] Fair: A few solids are attached

[0385] Bad: Many solids are attached.

[0386] The compounds used in Examples are as follows:

[0387] MDI-based blocked isocyanate: a compound obtained by blocking MDI (diphenylmethane diisocyanate) with methyl ethyl ketoxime

[0388] TDI-based blocked isocyanate: a compound obtained by blocking TDI (tolylene diisocyanate) with methyl ethyl ketoxime

[0389] HDI-based blocked isocyanate: a compound obtained by blocking HDI (hexamethylene diisocyanate) with 3,5-dimethylpyrazole

[0390] Acetylene glycol: 2,4,7,9-tetramethyl-5-decyne-4,7-diol

[0391] Polyoxyalkylene group-containing emulsifier: polyoxyethylene alkyl ether

Production Example 1

[0392] A 500 ml plastic container was charged with 30 g of a water-soluble glycol-based solvent, 30 g of stearic acid amide ethyl acrylate, 50 g of stearyl acrylate, 180 g of pure water, 2 g of a cationic emulsifier, 2 g of a sorbitan fatty acid ester, and 6 g of a polyoxyethylene alkyl ether. The components were heated to 80° C., stirred with a homomixer at 2,000 rpm for 1 minute, and then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred into a 500 ml autoclave, followed by nitrogen purge, and then 0.2 g of lauryl mercaptan and 20 g of vinyl chloride were added. Further, 1 g of an azo group-containing water-soluble initiator was added, the resulting mixture was heated to 60° C., and reacted for 4 hours to provide an aqueous dispersion of a polymer. The dispersion was diluted with pure water to prepare an aqueous dispersion having a solid concentration of 30%.

Production Examples 2 to 4

[0393] Polymerization was performed according to the composition shown in Table 1 in the same manner as in Production Example 1, and the polymer thus obtained was then diluted with pure water to prepare an aqueous dispersion having a solid concentration of 30%.

Production Example 5

[0394] A 500 ml plastic container was charged with 17 g of a water-soluble glycol-based solvent, 21 g of stearic acid amide ethyl acrylate, 9 g of palmitic acid amide ethyl acrylate, 30 g of stearyl acrylate, 120 g of pure water, 0.6 g of a cationic emulsifier, 1 g of a sorbitan fatty acid ester, and 4.4 g of a polyoxyethylene alkyl ether. The components were heated to 80° C., stirred with a homomixer at 2,000 rpm for 1 minute, and then ultrasonically emulsified and dispersed for 15 minutes. The emulsified dispersion was transferred into a 500 cc four-necked flask equipped with a nitrogen introduction tube, a thermometer, a stirring rod, and a reflux tube, followed by nitrogen purge, and then 0.1 g of lauryl mercaptan was added. After stirring, 0.6 g of an azo group-containing water-soluble initiator was further added, and the resulting mixture was heated to 60° C. and reacted for 4 hours to provide an aqueous dispersion of a polymer. Thereafter, pure water was added to prepare a water dispersion having a solid concentration of 30%.

Production Example 6

[0395] A 200 mL four-necked flask was charged with 14 g of methyl hydrogen silicon oil (SiH:SiCH.sub.3 molar ratio determined by 1H NMR=50:50) and 0.02 g of a hydrosilylation Pt catalyst. A stirring rod, a thermometer, and a reflux tube were installed thereon, and a dropping funnel was charged with 25 g of CH.sub.2═CH—(CH.sub.2CH.sub.2).sub.n—CH.sub.2CH.sub.3 (n=7). CH.sub.2═CH—(CH.sub.2CH.sub.2).sub.n—CH.sub.2CH.sub.3 (n=7) was added dropwise from the dropping funnel while the temperature was maintained at 70° C. After dropping was finished, the reaction was further continued at 70° C. for about 3 hours. Disappearance of the peak of SiH was confirmed by infrared spectroscopy (IR), and silicone polymer A was thus provided.

Production Examples 7 to 9

[0396] Synthesis was performed according to the composition shown in Table 2 in the same manner as in Production Example 6. Disappearance of the peak of SiH was confirmed by infrared spectroscopy (IR), and silicone polymers B to D were thus provided.

Production Example 10

[0397] A 250 ml plastic container was charged with 28 g of silicone polymer A, 5.6 g of a water-soluble glycol-based solvent, 50 g of pure water, 1.7 g of a sorbitan fatty acid ester, 0.7 g of a polyoxyethylene alkyl ether, and 0.6 g of a cationic emulsifier. The components were heated to 75° C., stirred with a homomixer at 2,000 rpm for 1 minute and then ultrasonically emulsified and dispersed for 10 minutes. An aqueous dispersion was thus provided. Thereafter, pure water was added to prepare a water dispersion having a solid concentration of 30%.

Production Examples 11 to 13

[0398] A water dispersion was provided according to the composition shown in Table 3 in the same manner as in Production Example 10, and then was diluted with pure water to prepare an aqueous dispersion having a solid concentration of 30%.

Production Example 14

[0399] In a high pressure reaction vessel, 150 g of paraffin wax (melting point: 66° C., needle penetration: 12 (25° C.)) 350 g of pure water, 4.5 g of polyoxyethylene alkyl ether, and 3 g of a sorbitan fatty acid ester were placed and sealed. The components were heated to 110 to 120° C. with stirring and then emulsified at high pressure for 30 minutes to provide an aqueous dispersion. Further, the solid content was adjusted with pure water to 30%.

Production Example 15

[0400] An aqueous dispersion was provided in the same manner as in Production Example 14 except that 150 g of paraffin wax (melting point: 75° C., needle penetration: 6 (25° C.)) was used in a high pressure reaction vessel. Further, the solid content was adjusted with pure water to 30%.

Production Example 16

[0401] An aqueous dispersion was provided in the same manner as in Production Example 15 except that 150 g of paraffin wax (melting point: 82° C., needle penetration: 5 (25° C.)) was used in a high pressure reaction vessel. Further, the solid content was adjusted with pure water to 30%.

TABLE-US-00002 TABLE 1 Prod. Prod. Prod. Prod. Prod. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Stearic acid amide ethyl acrylate 30 21 20 20 21 Palmitic acid amide ethyl acrylate — 9 9 9 9 Stearyl acrylate 50 50 50 50 30 Glycidyl methacrylate — — 1 — — Hydroxyethyl acrylate — — — 1 — Vinyl chloride 20 20 20 20 — Azo group-containing water-soluble 1 1 1 1 0.6 initiator Lauryl mercaptan 0.2 0.2 0.2 0.2 0.1 Water-soluble glycol-based solvent 30 30 30 30 17 Cationic emulsifier 2 2 2 2 0.6 Sorbitan fatty acid ester 2 2 2 2 1 Polyoxyethylene alkyl ether 6 6 6 6 4.4 Pure water 180 180 180 180 120 Numerals in table are in grams.

TABLE-US-00003 TABLE 2 Composition of silicone polymer molar ratio SiH:SiCH.sub.3 Prod. Prod. Prod. Prod. (1H NMR) Ex. 6 Ex. 7 Ex. 8 Ex. 9 Methyl hydrogen silicon oil 90:10 7.6 Methyl hydrogen silicon oil 60:40 12 Methyl hydrogen silicon oil 50:50 14 Methyl hydrogen silicon oil 30:70 17 CH.sub.2═CH—(CH.sub.2CH.sub.2), CH.sub.2CH.sub.3 (n = 14) 45 CH.sub.2═CH—(CH.sub.2CH.sub.2).sub.n—CH.sub.2CH.sub.3 (n = 11) 36 36 CH.sub.2═CH—(CH.sub.2CH.sub.2).sub.n—CH.sub.2CH.sub.3 (n = 7) 25 Hydrosilylation Pt catalyst 0.02 0.02 0.02 0.02 Numerals in the table are in grams

TABLE-US-00004 TABLE 3 Prod. Prod. Prod. Prod. Ex. 10 Ex. 11 Ex 12 Ex. 13 Silicone polymer A 28 Silicone polymer B 28 Silicone polymer C 28 Silicone polymer D 28 Water-soluble glycol-based solvent 5.6 5.6 5.6 5.6 Cationic emulsifier 0.6 0.6 0.6 0.6 Sorbitan fatty acid ester 1.7 1.7 1.7 1.7 Polyoxyethylene alkyl ether 0.7 0.7 0.7 0.7 Pure water 50 50 50 50

Example 1 (Test Example 1)

[0402] A test liquid (1,000 g) was prepared by diluting 50 g of the water dispersion having a solid concentration of 30% prepared in Production Example 2 and 5 g of the MDI-based blocked isocyanate (solid concentration: 20%) with tap water. A polyester fabric, a nylon fabric, and a cotton fabric were immersed in this test liquid and wrung with a mangle. The wet pickup was about 55% (polyester fabric), about 35% (nylon fabric), and about 55% (cotton fabric). The treated polyester fabric and the treated nylon fabric were dried and cured by passing through a pin tenter at 170° C. for 1 minute. The treated cotton fabric was dried and cured by passing through a pin tenter at 170° C. for 2 minutes.

[0403] The water-repellency of the test fabrics treated in this way was evaluated through a water-repellency test in accordance with the spray method of JIS L-1092. The results of the water-repellency are shown in Table 4.

[0404] Additionally, the evaluation results of the water-repellency of the test fabrics washed 20 times and then dried with a tumbler (at 60° C. for 30 minutes) in accordance with JIS L-0217103 are similarly shown in Table 4.

Examples 2 to 8 (Test Examples 2 to 8)

[0405] A test liquid (1,000 g) was prepared according to the formulation shown in Table 4 in the same manner as in Example 1 (Test Example 1). A polyester fabric, a nylon fabric, and a cotton fabric were immersed in this test liquid and wrung with a mangle. The wet pickup was about 55% (polyester fabric), about 35% (nylon fabric), and about 55% (cotton fabric). The treated polyester fabric and the treated nylon fabric were dried and cured by passing through a pin tenter at 170° C. for 1 minute. The treated cotton fabric was dried and cured by passing through a pin tenter at 170° C. for 2 minutes.

[0406] The water-repellency of the test fabrics treated in this way was evaluated through a water-repellency test in accordance with the spray method of JIS L-1092. The results of the water-repellency are shown in Table 4.

[0407] Additionally, the evaluation results of the water-repellency of the test fabrics washed 5 times or 20 times and then dried with a tumbler (at 60° C. for 30 minutes) in accordance with JIS L-0217103 are similarly shown in Table 4.

Example 9 (Test Example 9)

[0408] A test liquid (1,000 g) was prepared by diluting 50 g of the water dispersion having a solid concentration of 30% prepared in Production Example 2 and 0.5 g of acetylene group-containing glycol with tap water. A polyester fabric, a nylon fabric, and a cotton fabric were immersed in this test liquid and wrung with a mangle. The wet pickup was about 55% (polyester fabric), about 35% (nylon fabric), and about 55% (cotton fabric). The treated polyester fabric and the treated nylon fabric were dried and cured by passing through a pin tenter at 170° C. for 1 minute. The treated cotton fabric was dried and cured by passing through a pin tenter at 170° C. for 2 minutes.

[0409] The water-repellency of the test fabrics treated in this way was evaluated through a water-repellency test in accordance with the spray method of JIS L-1092. The results of the water-repellency are shown in Table 4.

Example 10 (Test Example 10)

[0410] A test liquid (1,000 g) was prepared by diluting 50 g of the water dispersion having a solid concentration of 30% prepared in Production Example 2 and 0.5 g of a polyoxyalkylene alkyl ether with tap water. A polyester fabric, a nylon fabric, and a cotton fabric were immersed in this test liquid and wrung with a mangle. The wet pickup was about 55% (polyester fabric), about 35% (nylon fabric), and about 55% (cotton fabric). The treated polyester fabric and the treated nylon fabric were dried and cured by passing through a pin tenter at 170° C. for 1 minute. The treated cotton fabric was dried and cured by passing through a pin tenter at 170° C. for 2 minutes.

[0411] The water-repellency of the test fabrics treated in this way was evaluated through a water-repellency test in accordance with the spray method of JIS L-1092. The results of the water-repellency are shown in Table 4.

Example 11 (Test Example 11)

[0412] A test liquid (1,000 g) was prepared by diluting 45 g of the water dispersion prepared in Production Example 2 and 5 g of the water dispersion prepared in Production Example 10 with tap water. A polyester fabric, a nylon fabric, and a cotton fabric were immersed in this test liquid and wrung with a mangle. The wet pickup was about 55% (polyester fabric), about 35% (nylon fabric), and about 55% (cotton fabric). The treated polyester fabric and the treated nylon fabric were dried and cured by passing through a pin tenter at 170° C. for 1 minute. The treated cotton fabric was dried and cured by passing through a pin tenter at 170° C. for 2 minutes.

[0413] The water-repellency of the test fabrics treated in this way was evaluated through a water-repellency test in accordance with the spray method of JIS L-1092. The results of the water-repellency are shown in Table 4.

Examples 12 to 19 (Test Examples 12 to 19)

[0414] A test liquid (1,000 g) was prepared according to the formulation shown in Table 4 in the same manner as in Example 11 (Test Example 11). A polyester fabric, a nylon fabric, and a cotton fabric were immersed in this test liquid and wrung with a mangle. The wet pickup was about 55% (polyester fabric), about 35% (nylon fabric), and about 55% (cotton fabric). The treated polyester fabric and the treated nylon fabric were dried and cured by passing through a pin tenter at 170° C. for 1 minute. The treated cotton fabric was dried and cured by passing through a pin tenter at 170° C. for 2 minutes.

[0415] The water-repellency of the test fabrics treated in this way was evaluated through a water-repellency test in accordance with the spray method of JIS L-1092. The results of the water-repellency are shown in Table 4.

Example 20 (Test Example 20)

[0416] A test liquid (1,000 g) was prepared by diluting 50 g of the water dispersion having a solid concentration of 30% prepared in Production Example 2, 5 g of the MDI-based blocked isocyanate (solid concentration: 20%), and 0.5 g of acetylene group-containing glycol with tap water. A polyester fabric, a nylon fabric, and a cotton fabric were immersed in this test liquid and wrung with a mangle. The wet pickup was about 55% (polyester fabric), about 35% (nylon fabric), and about 55% (cotton fabric). The treated polyester fabric and the treated nylon fabric were dried and cured by passing through a pin tenter at 170° C. for 1 minute. The treated cotton fabric was dried and cured by passing through a pin tenter at 170° C. for 2 minutes.

[0417] The water-repellency of the test fabrics treated in this way was evaluated through a water-repellency test in accordance with the spray method of JIS L-1092. The results of the water-repellency are shown in Table 4.

[0418] Additionally, the evaluation results of the water-repellency of the test fabrics washed 20 times and then dried with a tumbler (at 60° C. for 30 minutes) in accordance with JIS L-0217103 are similarly shown in Table 4.

Examples 21 to 24 (Test Examples 21 to 24)

[0419] A test liquid (1,000 g) was prepared according to the formulation shown in Table 4 in the same manner as in Example 20 (Test Example 20). A polyester fabric, a nylon fabric, and a cotton fabric were immersed in this test liquid and wrung with a mangle. The wet pickup was about 55% (polyester fabric), about 35% (nylon fabric), and about 55% (cotton fabric). The treated polyester fabric and the treated nylon fabric were dried and cured by passing through a pin tenter at 170° C. for 1 minute. The treated cotton fabric was dried and cured by passing through a pin tenter at 170° C. for 2 minutes.

[0420] The water-repellency of the test fabrics treated in this way was evaluated through a water-repellency test in accordance with the spray method of JIS L-1092. The results of the water-repellency are shown in Table 4.

[0421] Additionally, the evaluation results of the water-repellency of the test fabrics washed 20 times and then dried with a tumbler (at 60° C. for 30 minutes) in accordance with JIS L-0217103 are similarly shown in Table 4.

Comparative Example 1 (Comparative Test Example 1)

[0422] A test liquid (1,000 g) was prepared by diluting 50 g of the water dispersion having a solid concentration of 30% prepared in Production Example 1 with tap water. A polyester fabric, a nylon fabric, and a cotton fabric were immersed in this test liquid and wrung with a mangle. The wet pickup was about 55% (polyester fabric), about 35% (nylon fabric), and about 55% (cotton fabric). The treated polyester fabric and the treated nylon fabric were dried and cured by passing through a pin tenter at 170° C. for 1 minute. The treated cotton fabric was dried and cured by passing through a pin tenter at 170° C. for 2 minutes.

[0423] The water-repellency of the test fabrics treated in this way was evaluated through a water-repellency test in accordance with the spray method of JIS L-1092. The results of the water-repellency are shown in Table 4.

[0424] Additionally, the evaluation results of the water-repellency of the test fabrics washed 5 times or 20 times and then dried with a tumbler (at 60° C. for 30 minutes) in accordance with JIS L-0217103 are similarly shown in Table 4.

Comparative Examples 2 to 5 (Comparative Test Examples 2 to 5)

[0425] A test liquid (1,000 g) was prepared according to the formulation shown in Table 4 in the same manner as in Comparative Example 1 (Comparative Test Example 1). A polyester fabric, a nylon fabric, and a cotton fabric were immersed in this test liquid and wrung with a mangle. The wet pickup was about 55% (polyester fabric), about 35% (nylon fabric), and about 55% (cotton fabric). The treated polyester fabric and the treated nylon fabric were dried and cured by passing through a pin tenter at 170° C. for 1 minute. The treated cotton fabric was dried and cured by passing through a pin tenter at 170° C. for 2 minutes.

[0426] The water-repellency of the test fabrics treated in this way was evaluated through a water-repellency test in accordance with the spray method of JIS L-1092. The results of the water-repellency are shown in Table 4.

[0427] Additionally, the evaluation results of the water-repellency of the test fabrics washed 5 times or 20 times and then dried with a tumbler (at 60° C. for 30 minutes) in accordance with JIS L-0217103 are similarly shown in Table 4.

TABLE-US-00005 TABLE 4 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Formulation Water- Prod. Ex. 1 50 repellent Prod. Ex. 2 50 50 50 50 50 50 dispersion Prod. Ex. 3 50 Prod. Ex. 4 50 Prod. Ex. 5 50 Combination MDI-based blocked 5 5 5 5 5 agent isocyanate TDI-based blocked 5 isocyanate HDI-based blocked 5 isocyanate Melamine-based 5 resin Acetylene glycol 0.5 Polyoxyalkylene 0.5 alkyl ether Prod. Ex. 10 Prod. Ex. 11 Prod. Ex. 12 Prod. Ex. 13 Prod. Ex. 14 Prod. Ex. 15 Prod. Ex. 16 Evaluation Water- Polyester Initial 100 100 100 100 100 90- 90- 90-100 100 100 repellency 100 100 HL20 90 80-90 80 80-90 90 90 90 70 Nylon Initial 100 100 100 100 100 90- 90- 90-100 100 90-100 100 100 HL20 80 80 70-80 80 80 80 80 70 Cotton Initial 80-90 80-90 80-90 80-90 80-90 80 80 80-90 80 80 HL20 70 70 70 70 70 70 70 50 Gum-up property Fair Fair Fair Fair Fair Fair Fair Fair Good Good Ex. Ex. Ex. Ex. 11 Ex. 12 Ex. 13 Ex. 14 15 16 17 Ex. 18 Ex. 19 Formulation Water- Prod. Ex. 1 repellent Prod. Ex. 2 45 45 45 45 45 45 45 dispersion Prod. Ex. 3 Prod. Ex. 4 Prod. Ex. 5 45 45 Combination MDI-based blocked agent isocyanate TDI-based blocked isocyanate HDI-based blocked isocyanate Melamine-based resin Acetylene glycol Polyoxyalkylene alkyl ether Prod. Ex. 10 5 Prod. Ex. 11 5 5 Prod. Ex. 12 5 Prod. Ex. 13 5 Prod. Ex. 14 5 Prod. Ex. 15 5 5 Prod. Ex. 16 5 Evaluation Water- Polyester Initial 100 100 100 100 100 100 100 100 100 repellency HL20 Nylon Initial 100 100 100 100 100 100 100 100 90-100 HL20 Cotton Initial 90 90-100 90-100 90-100 80-90 90 90 90 80 HL20 Gum-up property Good Good Good Good Fair Fair Fair Good Fair Ex. Com. Com. Com. Com. Com. Ex. 20 Ex. 21 Ex. 22 Ex. 23 24 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Formulation Water- Prod. Ex. 1 50 repellent Prod. Ex. 2 50 50 45 45 45 50 dispersion Prod. Ex. 3 50 Prod. Ex. 4 50 Prod. Ex. 5 50 Combination MDI-based blocked 5 5 5 5 1.2 agent isocyanate TDI-based blocked 1.2 isocyanate HDI-based blocked 1.2 isocyanate Melamine-based 1.2 resin Acetylene glycol 0.5 0.25 Polyoxyalkylene 0.5 0.5 0.5 0.25 alkyl ether Prod. Ex. 10 Prod. Ex. 11 5 2.5 Prod. Ex. 12 Prod. Ex. 13 Prod. Ex. 14 Prod. Ex. 15 5 2.5 Prod. Ex. 16 Evaluation Water- Polyester Initial 100 100 100 100 100 100 100 90-100 90-100 90-100 repellency HL20 90 90 90 90 90 80 80 70-80 70-80 50 Nylon Initial 100 90-100 100 90-100 100 100 100 90-100 90-100 90-100 HL20 80 80 80 80 80 70-80 70-80 70-80 70-80 50 Cotton Initial 80-90 80-90 90-100 90 90-100 80 80 70 70 80 HL20 70 70 70 70 70 50 50 50 50 0-50 Gum-up property Good Good Good Good/Fair Good Good Good Fair Fair Fair Numerals in tables are in grams.

INDUSTRIAL APPLICABILITY

[0428] The water-repellent composition may be used as an external treatment agent (surface treatment agent) or an internal treatment agent. The water-repellent composition can be suitably used for substrates such as textile products and masonry and imparts excellent water-repellency to the substrates.