WATER REPELLENT AGENT COMPOSITION AND METHOD FOR PRODUCING WATER REPELLENT FIBER PRODUCT

Abstract

A water repellent agent composition contains a compound represented by the following General Formula (1) and a silicone resin:

##STR00001##

wherein in Formula (1), R.sup.31 represents a monovalent hydrocarbon group having 4 to 30 carbon atoms, R.sup.32 represents a hydrogen, a monovalent hydrocarbon group having 1 to 30 carbon atoms, or an organic group represented by —R.sup.36—N(R.sup.37)—R.sup.38 (in the formula, R.sup.36 represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and R.sup.37 and R.sup.38 each independently represent a hydrogen or a monovalent hydrocarbon group having 1 to 30 carbon atoms), R.sup.33 represents a divalent hydrocarbon group having 1 to 30 carbon atoms, R.sup.34 and R.sup.35 each independently represent a hydrogen or a monovalent hydrocarbon group having 1 to 30 carbon atoms, a represents an integer of 0 to 2, and when a is 2, the plurality of R.sup.32 and R.sup.33 each may be identical or different.

Claims

1. A water repellent agent composition comprising a compound represented by the following General Formula (1) and a silicone resin: ##STR00016## wherein in Formula (1), R.sup.31 represents a monovalent hydrocarbon group having 4 to 30 carbon atoms, R.sup.32 represents a hydrogen, a monovalent hydrocarbon group having 1 to 30 carbon atoms, or an organic group represented by —R.sup.36—N(R.sup.37)—R.sup.38 (in the formula, R.sup.36 represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and R.sup.37 and R.sup.38 each independently represent a hydrogen or a monovalent hydrocarbon group having 1 to 30 carbon atoms), R.sup.33 represents a divalent hydrocarbon group having 1 to 30 carbon atoms, R.sup.34 and R.sup.35 each independently represent a hydrogen or a monovalent hydrocarbon group having 1 to 30 carbon atoms, a represents an integer of 0 to 2, and when a is 2, the plurality of R.sup.32 and R.sup.33 each may be identical or different.

2. The water repellent agent composition according to claim 1, wherein a melting point or freezing point of the compound represented by the above General Formula (1) is 40° C. to 70° C.

3. A method for producing a water-repellent textile product, the method comprising a step of treating fibers with a treatment liquid including the water repellent agent composition according to claim 1.

4. A method for producing a water-repellent textile product, the method comprising a step of treating fibers with a treatment liquid including the water repellent agent composition according to claim 2.

Description

EXAMPLES

[0159] Hereinafter, the present invention will be described in more detail by way of Examples; however, the present invention is not intended to be limited by these Examples.

[0160] [Preparation of Dispersion Liquid]

Example 1

[0161] 10 parts by mass of MQ-1600 (trimethylsilyl group-containing polysiloxane, manufactured by Dow Corning Toray Co., Ltd., trade name) as the silicone resin was added to 10 parts by mass of MORESCO-WHITE P-40 (low-viscosity hydrocarbon, manufactured by MORESCO Corporation, trade name) and 10 parts by mass of DOW CORNING TORAY SH 200 FLUID 100cs (low-viscosity methylpolysiloxane, manufactured by Dow Corning Toray Co., Ltd., trade name) as the solvents and mixed until the silicone resin was dissolved, thereby obtaining a mixture. Subsequently, after it was confirmed that the mixture was uniform, 0.14 parts by mass of laurylamine as the compound (1) was added to the mixture, and the mixture was heated to dissolve the laurylamine. The mixed liquid after heating was cooled to room temperature. Subsequently, 0.75 parts by mass of SOFTANOL 50 (5-mol ethylene oxide adduct of branched alcohol having 12 to 14 carbon atoms, manufactured by NIPPON SHOKUBAI CO., LTD., trade name) and 0.75 parts by mass of SOFTANOL 90 (9-mol ethylene oxide adduct of branched alcohol having 12 to 14 carbon atoms, manufactured by NIPPON SHOKUBAI CO., LTD., trade name) as the non-ionic surfactants were mixed with the cooled mixture. Subsequently, 68.4 parts by mass of water as the aqueous medium was added to the mixture little by little, thereby obtaining a dispersion liquid.

Examples 2 to 16 and 19 to 21

[0162] Dispersion liquids were obtained in the similar manner to Example 1, except that compositions were changed to compositions (unit: parts by mass) presented in Tables 1 to 3. In the tables, the melting point (mp) or the freezing point (fp) of the compound (1) was presented.

Example 17

[0163] Into a 500 mL pressure-resistant flask, 30 g of stearyl acrylate, 10 g of lauryl acrylate, 20 g of chloroethylene, 5 g of 30-mol ethylene oxide adduct of 3-styrenated phenol, 3 g of ARQUAD T-28 (manufactured by Lion Corporation, trade name, stearyl trimethyl ammonium chloride), 25 g of tripropylene glycol, and 206.7 g of water were put, and mixed and stirred at 45° C. to obtain a mixed liquid. This mixed liquid was irradiated with ultrasonic waves to disperse the whole monomer by emulsification. Subsequently, 0.3 g of azobis(isobutylamidine) dihydrochloride was added to the mixed liquid and subjected to radical polymerization at 60° C. for 6 hours in a nitrogen atmosphere, thereby obtaining a non-fluorinated acrylic polymer dispersion liquid containing 20% by mass of a non-fluorinated acrylic polymer. Subsequently, 50 parts by mass of the obtained non-fluorinated acrylic polymer dispersion liquid containing 20% by mass of the non-fluorinated acrylic polymer was mixed with 50 parts by mass of the dispersion liquid obtained in Example 6, thereby obtaining a dispersion liquid.

Example 18

[0164] 10 parts by mass of MORESCO-WHITE P-40 and 10 parts by mass of DOW CORNING TORAY SH 200 FLUID 100cs were used as the solvent, 10 parts by mass of MQ-1600 as the silicone resin was added to the solvent and mixed until the silicone resin was dissolved, thereby obtaining a mixture. Subsequently, after it was confirmed that the mixture was uniform, 0.2 parts by mass of oleylamine as the compound (1) was added to the mixture, and the mixture was heated to dissolve the oleylamine Subsequently, the mixed liquid after heating was cooled to room temperature. Subsequently, 0.1 parts by mass of SF8417 as the amino-modified silicone was added to the cooled mixture and mixed. Thereafter, 0.75 parts by mass of SOFTANOL 50 and 0.75 parts by mass of SOFTANOL 90 as the non-ionic surfactants were added to the mixture and mixed. Subsequently, 68.2 parts by mass of water as the aqueous medium was added to the mixture little by little, thereby obtaining a dispersion liquid.

Comparative Example 1

[0165] A dispersion liquid was obtained in the similar manner to Example 6, except that the silicone resin was not added, and the amounts of MORESCO-WHITE P-40 and DOW CORNING TORAY SH 200 FLUID 100cs mixed were set to 15 parts by mass, respectively.

Comparative Example 2

[0166] The non-fluorinated acrylic polymer dispersion liquid containing 20% by mass of the non-fluorinated acrylic polymer obtained in Example 17 was used as the dispersion liquid without any changes.

Comparative Example 3

[0167] A dispersion liquid was obtained in the similar manner to Example 18, except that the compound (1) and MORESCO-WHITE P-40 were not added and the amounts of SF8417, DOW CORNING TORAY SH 200 FLUID 100cs, and water mixed were set to 2 parts by mass, 20 parts by mass, and 66.5 parts by mass, respectively.

Comparative Example 4

[0168] A dispersion liquid was obtained in the similar manner to Example 1, except that the compound (1) was not added and the amount of water mixed was set to 68.5 parts by mass.

Comparative Example 5

[0169] 0.75 parts by mass of SOFTANOL 50 and 0.75 parts by mass of SOFTANOL 90 as the non-ionic surfactants were mixed with 30 parts by mass of SF8417 as the amino-modified silicone, thereby obtaining a mixture. Subsequently, 68.5 parts by mass of water was added to the mixture little by little, thereby obtaining a dispersion liquid.

[0170] (Water Repellency Evaluation of Water-Repellent Textile Product)

[0171] A test was performed according to the spray method of JIS L 1092 (2009) at a shower water temperature of 20° C. In the present test, a 100% polyester fabric or 100% nylon fabric which had been dyed was subjected to an immersion treatment (pickup rate: 60% by mass) in a treatment liquid obtained by diluting each of the dispersion liquids obtained in Examples and Comparative Examples with water such that the content of the dispersion liquid would be 3% by mass, and then the fabric was dried at 130° C. for 1 minute. Further, in the 100% polyester fabric, the fabric was heat-treated at 180° C. for 30 seconds, and in the 100% nylon fabric, the fabric was heat-treated at 170° C. for 30 seconds, thereby obtaining a water-repellent textile product. The water repellency of the water-repellent textile product thus obtained was evaluated. The results were evaluated by the following criteria by visual inspection. Incidentally, a case in which the property was between Grade 4 and Grade 5 was designated as “4-5”. The results are presented in Tables 1 to 4.

[0172] Water repellency: state

[0173] 5: There is no moisture adhering to the surface.

[0174] 4: There is slight moisture adhering to the surface.

[0175] 3: The surface shows partial wetting.

[0176] 2: The surface shows wetting.

[0177] 1: The entire surface shows wetting.

[0178] 0: Both the front surface and the back surface show complete wetting.

[0179] (Durable Water Repellency Evaluation of Water-Repellent Textile Product)

[0180] A test was performed according to the spray method of JIS L 1092 (2009) at a shower water temperature of 20° C. In the present test, a 100% polyester fabric or 100% nylon fabric, which had been dyed, was subjected to an immersion treatment (pickup rate: 60% by mass) in a treatment liquid obtained by diluting each of the dispersion liquids of Examples and Comparative Examples and each of the above-described chemical agents with water such that each of the dispersion liquids obtained in each of Examples and Comparative Examples would be 3% by mass, NK ASSIST NY-50 (manufactured by NICCA CHEMICAL CO., LTD., trade name) as the blocked isocyanate-based crosslinking agent would be 1% by mass, TEXPORT BG-290 (manufactured by NICCA CHEMICAL CO., LTD., trade name) as the penetrant would be 1% by mass, and NICEPOLE FE-26 (manufactured by NICCA CHEMICAL CO., LTD., trade name) as the antistatic agent would be 0.5% by mass, and then the fabric was dried at 130° C. for 1 minute. Further, in the 100% polyester fabric, the fabric was heat-treated at 180° C. for 30 seconds, in the 100% nylon fabric, the fabric was heat-treated at 170° C. for 30 seconds, the obtained fabric was washed by the 103 method of JIS L 0217 (1995) 10 times (L-10), and the water repellency after air drying was evaluated in the similar manner to the water repellency evaluation method described above. The results are presented in Tables 1 to 4.

[0181] (Texture Evaluation of Water-Repellent Textile Product)

[0182] The texture of the water-repellent textile product obtained in the water repellency evaluation of the water-repellent textile product was evaluated on the basis of handling. The texture was evaluated by the following five grades. The results are presented in Tables 1 to 4.

[0183] 1: Hard˜5: Soft

[0184] (Evaluation of Peeling Strength with Respect to Water-Repellent Textile Product)

[0185] A test was performed according to JIS K 6404-5 (1999). First, each of the dispersion liquids obtained in Examples and Comparative Examples was diluted with water such that the dispersion liquid would be 3% by mass and NK ASSIST NY-50 (manufactured by NICCA CHEMICAL CO., LTD.) as the crosslinking agent would be 1% by mass, thereby preparing a treatment liquid. Subsequently, the dyed 100% nylon fabric was subjected to an immersion treatment (pickup rate: 60% by mass) using the obtained treatment liquid. Subsequently, the fabric subjected to the immersion treatment was dried at 130° C. for 2 minutes and further heat-treated at 160° C. for 30 seconds, thereby obtaining a base fabric. A seam tape (“MELCO tape” manufactured by SAN CHEMICALS, LTD.) was thermally adhered to the base fabric thus obtained at 150° C. for 1 minute using a thermocompression bonding apparatus, and the interlayer peeling strength between the base fabric and the seam tape was measured with an autograph (AG-IS, manufactured by SHIMADZU CORPORATION). The base fabric and the tape were pulled at a movement speed of the clamping jaws of 100 mm/min, and the average value of stress was designated as the peeling strength [N/inch]. The results are presented in Tables 1 to 4.

[0186] (Seam Slippage Property Evaluation of Water-Repellent Textile Product)

[0187] The seam slippage resistance of the water-repellent textile product obtained in the water repellency evaluation of the water-repellent textile product was measured by 8.23 Slippage Resistance 8.23.1 Seam Slippage Method b) B Method of JIS L 1096:2010. A smaller numerical value indicates that the water-repellent textile product is excellent in seam slippage property. In particular, the case of 4 mm or less was evaluated to be favorable. The results are presented in Tables 1 to 4.

TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4 Compound (1) Laurylamine (mp: 28° C.) 0.14 — — — Stearylamine (mp: 53° C.) — 0.05 0.1 0.2 Cetylamine (fp: 47° C.) — — — — Oleylamine (fp: 15° C.) — — — — Behenylamine (fp: 55° C. to 65° C.) — — — — 3-(Stearylamino)propylamine — — — — (mp: 30° C. to 40° C.) Distearylamine (mp: 60° C. to — — — — 70° C.) Silicone resin MQ-1600 10 10 10 10 Amino-modified SF8417 — — — — silicone Solvent MORESCO-WHITE P-40 10 10 10 10 DOW CORNING TORAY SH 10 10 10 10 200 FLUID 100 cs Non-ionic SOFTANOL 50 0.75 0.75 0.75 0.75 surfactant SOFTANOL 90 0.75 0.75 0.75 0.75 Non-fluorinated acrylic polymer — — — — Aqueous medium Water 68.4 68.5 68.4 68.3 Water repellency (polyester) Washing 0 times (L-0) 4-5 4-5 5 5 Durable water repellency Washing 10 times 3-4 3 4-5 4-5 (polyester) (L-10) Water repellency (nylon) Washing 0 times (L-0) 4 4-5 5 5 Durable water repellency Washing 10 times 2-3 2-3 2-3 2-3 (nylon) (L-10) Texture (polyester) 4 4 4 4 Peeling strength (nylon) (N/inch) 12.7 10.2 11.1 11.2 Seam slippage property (nylon) (mm) 2.2 2.2 2.3 2.3 Example 5 Example 6 Example 7 Example 8 Compound (1) Laurylamine (mp: 28° C.) — — — — Stearylamine (mp: 53° C.) 0.3 0.5 1 2 Cetylamine (fp: 47° C.) — — — — Oleylamine (fp: 15° C.) — — — — Behenylamine (fp: 55° C. to 65° C.) — — — — 3-(Stearylamino)propylamine — — — — (mp: 30° C. to 40° C.) Distearylamine (mp: 60° C. to — — — — 70° C.) Silicone resin MQ-1600 10 10 10 10 Amino-modified SF8417 — — — — silicone Solvent MORESCO-WHITE P-40 10 10 10 10 DOW CORNING TORAY SH 10 10 10 10 200 FLUID 100 cs Non-ionic SOFTANOL 50 0.75 0.75 0.75 0.75 surfactant SOFTANOL 90 0.75 0.75 0.75 0.75 Non-fluorinated acrylic polymer — — — — Aqueous medium Water 68.2 68.0 67.5 66.5 Water repellency (polyester) Washing 0 times (L-0) 5 5 4-5 4 Durable water repellency Washing 10 times 4-5 4-5 3-4 3 (polyester) (L-10) Water repellency (nylon) Washing 0 times (L-0) 5 5 4-5 3-4 Durable water repellency Washing 10 times 3 3 2-3 2-3 (nylon) (L-10) Texture (polyester) 4 4 4 4 Peeling strength (nylon) (N/inch) 12.1 11.5 11.2 11.2 Seam slippage property (nylon) (mm) 2.4 2.3 2.4 2.3

TABLE-US-00002 TABLE 2 Example 9 Example 10 Example 11 Example 12 Example 13 Compound (1) Laurylamine (mp: 28° C.) — — — — — Stearylamine (mp: 53° C.) — — — — — Cetylamine (fp: 47° C.) 0.09 — — — — Oleylamine (fp: 15° C.) — 0.2 — — — Behenylamine (fp: 55° C. to 65° C.) — — 0.24 — — 3-(Stearylamino)propylamine — — — 0.1 — (mp: 30° C. to 40° C.) Distearylamine (mp: 60° C. to — — — — 0.4 70° C.) Silicone resin MQ-1600 10 10 10 10 10 Amino-modified SF8417 — — — — — silicone Solvent MORESCO-WHITE P-40 10 10 10 10 10 DOW CORNING TORAY SH 10 10 10 10 10 200 FLUID 100 cs Non-ionic SOFTANOL 50 0.75 0.75 0.75 0.75 0.75 surfactant SOFTANOL 90 0.75 0.75 0.75 0.75 0.75 Non-fluorinated acrylic polymer — — — — — Aqueous medium Water 68.4 68.3 68.3 68.4 68.1 Water repellency (polyester) Washing 0 times (L-0) 4-5 3-4 4-5 4-5 3-4 Durable water repellency Washing 10 times 3 3 3 3 3 (polyester) (L-10) Water repellency (nylon) Washing 0 times (L-0) 4-5 5 5 5 5 Durable water repellency Washing 10 times 2-3 2-3 2-3 2-3 2-3 (nylon) (L-10) Texture (polyester) 4 4 4 4 4 Peeling strength (nylon) (N/inch) 11.1 11.1 10.9 10.8 10.9 Seam slippage property (nylon) (mm) 2.3 2.1 2.4 2.3 2.3 Example 14 Example 15 Example 16 Compound (1) Laurylamine (mp: 28° C.) — — — Stearylamine (mp: 53° C.) 0.5 0.5 0.5 Cetylamine (fp: 47° C.) — — — Oleylamine (fp: 15° C.) — — — Behenylamine (fp: 55° C. to 65° C.) — — — 3-(Stearylamino)propylamine — — — (mp: 30° C. to 40° C.) Distearylamine (mp: 60° C. to — — — 70° C.) Silicone resin MQ-1600 10 10 6 Amino-modified SF8417 — — — silicone Solvent MORESCO-WHITE P-40 20 — 12 DOW CORNING TORAY SH — 20 12 200 FLUID 100 cs Non-ionic SOFTANOL 50 0.75 0.75 0.75 surfactant SOFTANOL 90 0.75 0.75 0.75 Non-fluorinated acrylic polymer — — — Aqueous medium Water 68.0 68.0 68.0 Water repellency (polyester) Washing 0 times (L-0) 5 5 5 Durable water repellency Washing 10 times 4-5 4-5 4-5 (polyester) (L-10) Water repellency (nylon) Washing 0 times (L-0) 5 5 5 Durable water repellency Washing 10 times 3 3 3 (nylon) (L-10) Texture (polyester) 4 3-4 4 Peeling strength (nylon) (N/inch) 11.6 11.4 11.3 Seam slippage property (nylon) (mm) 2.3 2.3 2.3

TABLE-US-00003 TABLE 3 Example 17 Example 18 Example 19 Example 20 Example 21 Compound (1) Laurylamine (mp: 28° C.) — — — — — Stearylamine (mp: 53° C.) 0.25 — 0.2 — — Cetylamine (fp: 47° C.) — — — — — Oleylamine (fp: 15° C.) — 0.2 — 0.12 — Behenylamine (fp: 55° C. to 65° C.) — — — 0.12 0.12 3-(Stearylamino)propylamine — — — — — (mp: 30° C. to 40° C.) Distearylamine (mp: 60° C.to — — — — — 70° C.) Dimethylstearylamine (mp: 20° C.to 23° C.) — — 0.2 — 0.12 Silicone resin MQ-1600 5 10 10 10 10 Amino-modified SF8417 — 0.1 — — — silicone Solvent MORESCO-WHITE P-40 5 10 10 10 10 DOW CORNING TORAY SH 5 10 10 10 10 200 FLUID 100 cs Non-ionic SOFTANOL 50 0.38 0.75 0.75 0.75 0.75 surfactant SOFTANOL 90 0.38 0.75 0.75 0.75 0.75 Non-fluorinated acrylic polymer 10 — — — — Aqueous medium Water 74.0 68.2 68.1 68.3 68.3 Water repellency (polyester) Washing 0 times (L-0) 5 4-5 5 4-5 4-5 Durable water repellency Washing 10 times 4-5 3-4 4-5 3 3 (polyester) (L-10) Water repellency (nylon) Washing 0 times (L-0) 5 5 5 5 5 Durable water repellency Washing 10 times 3-4 2-3 2-3 2-3 2-3 (nylon) (L-10) Texture (polyester) 3-4 5 4 4 4 Peeling strength (nylon) (N/inch) 10.8 10.5 11.0 10.7 10.8 Seam slippage property (nylon) (mm) 2.3 2.1 2.2 2.3 2.2

TABLE-US-00004 TABLE 4 Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Compound (1) Laurylamine (mp: 28° C.) — — — — — Stearylamine (mp: 53° C.) 0.5 — — — — Cetylamine (fp: 47° C.) — — — — — Oleylamine (fp: 15° C.) — — — — — Behenylamine (fp: 55° C.to 65° C.) — — — — — 3-(Stearylamino)propylamine — — — — — (mp: 30° C.to 40° C.) Distearylamine (mp: 60° C. to — — — — — 70° C.) Silicone resin MQ-1600 — — 10 10 — Amino-modified SF8417 — — 2 — 30 silicone Solvent MORESCO-WHITE P-40 15 — — 10 — DOW CORNING TORAY SH 15 — 20 10 — 200 FLUID 100 cs Non-ionic SOFTANOL 50 0.75 — 0.75 0.75 0.75 surfactant SOFTANOL 90 0.75 — 0.75 0.75 0.75 Non-fluorinated acrylic polymer — 20 — — — Aqueous medium Water 68.0 80.0 66.5 68.5 68.5 Water repellency (polyester) Washing 0 times (L-0) 2 4 5 1 1 Durable water repellency Washing 10 times 1 2 4 1 1 (polyester) (L-10) Water repellency (nylon) Washing 0 times (L-0) 2 4 4-5 1 1 Durable water repellency Washing 10 times 1 2 4-5 1 1 (nylon) (L-10) Texture (polyester) 3-4 2 4 4 5 Peeling strength (nylon) (N/inch) 11.2 8.2 2.1 18.3 1.5 Seam slippage property (nylon) (mm) 6.2 8.4 2.9 2.8 12.1

[0188] It was confirmed that the water-repellent textile products treated with the water repellent agent compositions of Examples 1 to 21 are excellent in water repellency, durable water repellency, texture, and peeling strength and also excellent in seam slippage property.