JP2000080568A - Electrostatic and water repelling finishing of nylon fiber fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a nylon fiber fabric having both electrostatic property and water-repellency which are excellent in washing resistance by imparting a specific electrostatic agent to a nylon fiber fabric, subsequently treating the fiber in an acidic aqueous solution and then imparting a fluorine-containing water repelling agent. SOLUTION: An electrostatic agent consisting of a polyol containing an alkylene oxide such as a polyether polyol and an addition polymer of isocyanate, for example, a urethane oligomer in an amount of 0.5-1.0 wt.% is imparted to a nylon fiber fabric, and it is treated in an acidic aqueous solution, for example, a citric acid aqueous solution of pH 2-6. Subsequently, a fluorine-containing water-repelling agent consisting of a copolymer of a perfluoro group-containing acrylate or methacrylate or a copolymer of a compound copolymerizable therewith in an amount of 0.5-1.0 wt.% is imparted to the above fabric to perform an electrostatic and water repelling finishing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a nylon-based fiber cloth having excellent antistatic properties and water repellency having excellent washing durability.

[0002]

2. Description of the Related Art Conventionally, synthetic fibers are compared with natural fibers.
Static electricity is easily generated, and the tendency is particularly remarkable for nylon fiber fabrics. There are problems such as electric shock, clinging to the body, and contamination by dust in the air due to static electricity when sewing or wearing the product. In addition, nylon fiber fabrics are often used for outer clothing, and if not subjected to water repellent treatment, there is a problem that clothes are wet by rain, snow, etc., and a nylon fiber fabric having both antistatic performance and water repellency is provided. The development of was desired.

Conventionally, various methods have been proposed to address the above-mentioned problems. For example, regarding antistatic processing, a method of forming a complex on the fiber surface by treating it with an ionic polymer activator, or applying a mixture of a hydrophilic polymer substance and an acidic, basic or amide type low molecular substance to the fiber Then, a method of grafting to the fiber surface by dry heat, wet heat, radiation, microwave, ultraviolet light, etc., and further, a polymerizable monomer containing a block polymer of ethylene glycol and propylene glycol and having a terminal group composed of acrylic or methacrylic or A method has been proposed in which a prepolymer or the like containing a block polymer of ethylene glycol and propylene glycol and having a crosslinkable functional group at a terminal group is resinized on fibers alone or in combination with a crosslinking agent.

[0004] On the other hand, the water repellent treatment is usually carried out by impregnating a cloth with a water repellent such as a fluorine water repellent or a silicon water repellent in a final finishing step, and then performing a dry heat treatment. In particular, water-repellent processing using a fluorine-based water-repellent excellent in washing durability has been performed in many cases.

As a method of processing a synthetic fiber cloth having both antistatic performance and water repellency, for example, Japanese Patent Application Laid-Open No. 6-31687.
As described in Japanese Patent Publication No. 2, there is a method of forming a polyetherester resin layer on the surface of a synthetic fiber fabric, and then forming a fluorine-based water-repellent coating layer containing a cationic or anionic antistatic agent. However, there is a problem that practically sufficient durability cannot be easily obtained because the antistatic agent is contained in the fluorine-based water repellent film layer.

In Japanese Patent Application Laid-Open No. 6-158534, a treatment liquid containing a polyethylene glycol resin and a water-soluble polyester resin is applied to a polyester fiber, dried, and then treated with low-temperature plasma of a non-polymerizable gas. Although a method of performing water repellent processing after that is described, there is a problem that a special plasma processing apparatus is required.

[0007] It is difficult to obtain a performance satisfying both the antistatic performance and the water repellency. For example, if the amount of the antistatic agent used is increased to obtain a sufficient antistatic performance, the water repellency decreases. There is a problem, especially in the case of nylon fiber fabrics, in which the tendency is greater than polyester fibers, and at present, nylon fiber fabrics having both antistatic performance and water repellency having excellent washing durability have not been developed. .

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and provides a method of processing a nylon-based fiber cloth having both antistatic performance and water repellency having excellent washing durability. To provide.

[0009]

The present invention achieves the above object and has the following construction. That is, the present invention provides a first method of providing an electrostatic treatment agent comprising an addition polymer of an alkylene oxide-containing polyol and an isocyanate in an amount of 0.5 to 1% by weight to a nylon fiber cloth.
A second step of treating the fabric in an acidic aqueous solution, and adding a water-repellent treating agent comprising a copolymer with a perfluoroalkyl group-containing acrylate or methacrylate or a compound copolymerizable thereto to the fabric. The present invention provides a durable antistatic / water-repellent processing method for a nylon-based fiber fabric, which comprises a third step of providing a coating of about 1% by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The nylon-based fiber cloth used in the present invention is generally called polyamide fiber, and is made of nylon 6, nylon 6,.
6, Nylon 4.6, Nylon 6.10, Nylon 1
1, a woven fabric, a knitted fabric, and a non-woven fabric using 50% or more of fibers formed into a fiber by a fiber-forming polyamide polymer such as nylon 12 by a melt spinning method. Nylon fiber cloth is desizing, scouring, setting, and bleaching may be performed by a conventional method, and a bleached cloth may be used. Further, a dyed and fixed color cloth may be used. It is better to use a treated fabric. The term “fix treatment” as used herein means to apply a natural tannic acid derivative, a synthetic tannic acid derivative, an aromatic sulfonic acid condensate, or the like to the surface of a nylon fiber cloth by an exhaustion method or a pad dry method.

In the present invention, a first step of imparting an addition polymer of an alkylene oxide-containing polyol and an isocyanate to the above-mentioned nylon fiber cloth is performed. As the alkylene oxide-containing polyol used here, specifically, adipic acid, maleic acid, polyester polyol obtained by condensation polymerization of phthalic acid and alkylene glycol, polyalkylene glycol, obtained by condensation polymerization of alkylene oxide and higher alcohol Polyols such as polyether polyols can be mentioned.

Specific examples of the isocyanate used here include aromatic isocyanates such as tolylene diisocyanate and aliphatic isocyanates such as hexamethylene diisocyanate.

In the present invention, an addition polymer of the above-mentioned alkylene oxide-containing polyol and isocyanate is applied to a nylon-based fiber cloth. An addition polymer of an alkylene oxide-containing polyol and an isocyanate is a blocked isocyanate group in which an isocyanate group at a molecular chain end is protected by an inorganic salt or organic compound obtained by condensation polymerization of an alkylene oxide-containing polyol and an isocyanate, such as carbamoyl Examples include urethane oligomers that are sulfonate groups.
The use amount of the above-mentioned addition polymer is preferably in the range of 0.5 to 1% by weight. If the applied amount is less than 0.5% by weight, the desired antistatic performance cannot be obtained, and the applied amount is 1% by weight.
If it exceeds, sufficient water repellency cannot be obtained.

The method of applying the antistatic treatment agent containing the addition polymer to the nylon fiber cloth may be a commonly used padding method. The fiber cloth is immersed, squeezed uniformly with two mangles, and then dried. Drying conditions vary depending on the type of blocking agent used, but are preferably in the range of 70 to 120 ° C for 1 to 3 minutes.

Next, in the present invention, a second step of treating the nylon fiber fabric obtained by the above method with an acidic aqueous solution is performed. As the acidic aqueous solution used in the present invention, those which exhibit acidity when dissolved in water, specifically, organic acids such as citric acid, malic acid, and oxalic acid, and inorganic acids such as nitric acid, phosphoric acid, formic acid, hydrochloric acid, and sulfuric acid. Is an aqueous solution in which is dissolved.
The acid concentration used is preferably pH 2 to 6, more preferably pH 2 to 4. As a treatment method with an acidic aqueous solution,
A method of washing in an acidic aqueous solution using a continuous processing machine such as an open soaper or a liquid jet dyeing machine can be used.

Thereafter, in the present invention, a third step of applying a water-repellent treating agent comprising a copolymer with a perfluoroalkyl group-containing acrylate or methacrylate or a compound copolymerizable thereto to the fabric is performed. The perfluoroalkyl group-containing acrylate and methacrylate used in the present invention are represented by the following general formula 1 and are compounds that impart water repellency to fibers.

[0017]

Embedded image (Where R ₁ is hydrogen or a lower alkyl group, R _f is C _m
F _{2m + 1} , m is a perfluoroalkyl group represented by an integer of 2 to 21, and n is an integer of 10 to 200. )

The compound copolymerizable with the compound represented by the above general formula includes acrylic acid, methacrylic acid,
And vinyl compounds such as styrene and vinyl chloride. The amount of the perfluoroalkyl group-containing acrylate or methacrylate or the compound copolymerizable therewith is preferably in the range of 0.5 to 1% by weight based on the nylon fiber fabric. If it is less than 0.5% by weight, sufficient water repellency cannot be obtained, and if it exceeds 1% by weight, the texture of the nylon fiber fabric becomes hard, which is not preferable. In order to improve the water repellency of the fiber cloth, a melamine-based crosslinking agent or an isocyanate-based crosslinking agent may be used in combination. As a method of applying the treatment liquid containing the above-described water-repellent treatment agent to the nylon-based fiber cloth, a commonly used padding method may be used, and the nylon-based fiber cloth is immersed in the water-repellent treatment liquid. After uniformly squeezing with two mangles, dry and heat treat. The drying conditions are preferably from 70 to 120 ° C for 1 to 3 minutes, and the heat treatment conditions are preferably from 160 to 180 ° C for 0.5 to 2 minutes. The present invention has the above configuration.

[0019]

According to the present invention, when an addition polymer of an alkylene oxide-containing polyol and an isocyanate is applied to a nylon fiber fabric as in the present invention, a water-insoluble resin film having a hydrophilic molecular alkylene oxide in the molecule is formed.
The accumulation of static electricity generated by friction is suppressed, and the formed film firmly adheres to the fibers and exhibits excellent durability and antistatic performance against washing and the like. Furthermore, when the above-mentioned nylon fiber fabric is treated in an acidic aqueous solution, the addition polymer of the uncrosslinked alkylene oxide-containing polyol and the isocyanate on the surface of the nylon fiber fabric is washed and removed, and the decrease in the antistatic performance due to washing is reduced. . In addition, when a perfluoroalkyl group-containing acrylate, a methacrylate or a copolymer with a compound copolymerizable with them is provided, not only a nylon fiber fabric is imparted with durable water repellency but also an alkylene oxide-containing polyol. The addition polymer with the isocyanate is prevented from detaching from the nylon fiber cloth. By combining these effects, it is possible to obtain a well-balanced antistatic performance and water-repellent performance, and also excellent durability against washing and the like.

[0020]

Next, the present invention will be described in more detail with reference to Examples.
A sample after washing 10 times according to SL-1027 (103 method) was measured and evaluated by the following method. Antistatic performance Friction charge voltage JIS L-1094 B method Water repellency JIS L-1092 method Spray method

Example 1 Nylon false twisted yarn 70d / 34f was subjected to warp (warp density:
208 yarns / inch), nylon false twisted yarn 155d / 96
f was used for the weft (weft density: 77 yarns / inch), and a plain-textured nylon fabric was woven. After scouring, relaxing, and presetting the nylon fabric according to a conventional method, it is dyed with a dyeing solution of the following formulation 1 at 100 ° C. for 30 minutes, and further subjected to a fixing treatment of the following formulation 2 at 80 ° C. for 20 minutes. At 80 ° C. for 5 minutes. [Formulation 1] Suminol Mill Red RS 2% owf (manufactured by Sumitomo Chemical Co., Ltd., acid dye) Leveran NKD 2% owf (Marubishi Yuka Kogyo Co., Ltd., leveling agent) Acetic acid (48%) 2 cc / liter [Prescription 2] Nikka Sun Life E-37 2% owf (fixing agent, manufactured by Nikka Chemical Co., Ltd.) Next, immersed in a urethane oligomer solution having the following prescription 3
The mixture was uniformly squeezed with a mangle at a squeezing ratio of 60%, and dried and heat-treated at 160 ° C. for 1 minute using a heat setter. [Prescription 3] Elastron W-33 30 g / liter (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., urethane oligomer-based antistatic agent, solid content: 30%) Sodium bicarbonate 1.5 g / liter After washing in an aqueous solution containing 1 g / liter of citric acid at 40 ° C. for 5 minutes, it was dried at 160 ° C. for 1 minute. Next, it was immersed in a fluorine-based water repellent solution having the following formulation 4 and uniformly squeezed with a mangle at a squeezing ratio of 50%.
After drying at 0 ° C. for 1 minute, finishing setting was performed at 170 ° C. for 1 minute to obtain a nylon fabric of Example 1. [Prescription 4] Paraguard 823 100 g / l (Ohara Palladium Chemical Co., Ltd., fluorine-based water repellent, solid content 20%) Paracat PGW 15 g / l (Ohara Palladium Chemical Co., Ltd., block isocyanate crosslinking agent) Sumi Tex Resin M-3 3 g / l (melamine cross-linking agent, manufactured by Sumitomo Chemical Co., Ltd.) Sumitex Accelerator ACX 3 g / l (cross-linking accelerator, manufactured by Sumitomo Chemical Co., Ltd.) Isopropyl alcohol 30 g / l

Example 2 A nylon woven fabric of Example 2 was obtained in the same manner as in Example 1 except that the same woven fabric as in Example 1 was used and that the formulation 3 was replaced with the formulation 5. [Prescription 5] Elastron W-33 50 g / liter (Daiichi Kogyo Seiyaku Co., Ltd., urethane oligomer-based antistatic agent, solid content 30%) Sodium bicarbonate 3 g / liter

Comparative Example 1 For comparison with the present invention, the same woven fabric as in Example 1 was used.
A nylon fabric of Comparative Example 1 was obtained in exactly the same manner as in Example 1 except that Formulation 3 was replaced with Formulation 6. [Prescription 6] Elastron W-33 20 g / liter (Daiichi Kogyo Seiyaku Co., Ltd., urethane oligomer-based antistatic agent, solid content 30%) Sodium bicarbonate 1 g / liter

Comparative Example 2 For comparison with the present invention, the processing of Comparative Example 2 was carried out in exactly the same manner as in Example 1 except that the same woven fabric as in Example 1 was used and that Formula 3 was replaced with Formula 7. A woven fabric was obtained. [Formulation 7] Elastron W-33 60 g / liter (Daiichi Kogyo Seiyaku Co., Ltd., urethane oligomer-based antistatic agent, solid content 30%) Sodium bicarbonate 4 g / liter Examples 1, 2 and Comparative Examples 1, 2 The performance of the processed fabric was measured and evaluated, and the results are shown in Table 1.

[0025]

[Table 1]

As is clear from Table 1, the processed fabrics of Examples 1 and 2 have a water repellency of 80 points or more and a friction band voltage of 2000 V or less even after 10 washes, and have excellent washing durability. It can be seen that it has both antistatic properties and antistatic properties. On the other hand, the processed fabric of Comparative Example 1 had poor antistatic properties, and the processed fabric of Comparative Example 2 had insufficient water repellency after 10 washes.

Example 3 A nylon fabric of Example 3 was obtained in the same manner as in Example 1 except that the same woven fabric as in Example 1 was used and that the formulation 3 was replaced with the formulation 9. [Prescription 9] Elastron W-33 40 g / liter (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane oligomer-based antistatic agent, solid content 30%) Sodium bicarbonate 2 g / liter

Example 4 The nylon fabric of Example 4 was prepared in the same manner as in Example 1 except that the same woven fabric as in Example 1 was used, and the formulation 3 was replaced with the formulation 9 and the formulation 4 was replaced with the formulation 10. Obtained. [Prescription 10] Paraguard 823 50 g / liter (Ohara Palladium Chemical Co., Ltd., fluorine water repellent, solid content 20%) Paracat PGW 8 g / liter (Ohara Palladium Chemical Co., Ltd., block isocyanate crosslinking agent) Sumi Tex Resin M-3 3 g / l (melamine-based crosslinking agent manufactured by Sumitomo Chemical Co., Ltd.) Sumitex Accelerator ACX 3 g / l (cross-linking accelerator manufactured by Sumitomo Chemical Co., Ltd.) Isopropyl alcohol 30 g / l

Comparative Example 3 For comparison with the present invention, the same woven fabric as in Example 1 was used.
A nylon fabric of Comparative Example 3 was obtained in the same manner as in Example 1, except that Formula 3 was replaced with Formula 9 and Formula 4 was replaced with Formula 11. [Prescription 11] Paragard 823 40 g / L (Ohara Palladium Chemical Co., Ltd., fluorine water repellent, solid content 20%) Paracat PGW 6 g / L (Ohara Palladium Chemical Co., Ltd., block isocyanate crosslinking agent) Sumi Tex Resin M-3 3 g / l (melamine-based crosslinking agent manufactured by Sumitomo Chemical Co., Ltd.) Sumitex Accelerator ACX 3 g / l (cross-linking accelerator manufactured by Sumitomo Chemical Co., Ltd.) Isopropyl alcohol 30 g / l

Comparative Example 4 For comparison with the present invention, the same woven fabric as in Example 1 was used.
A nylon fabric of Comparative Example 4 was obtained in exactly the same manner as in Example 1, except that Formula 3 was replaced with Formula 9 and Formula 4 was replaced with Formula 12. [Prescription 12] Paraguard 823 120 g / liter (Ohara Palladium Chemical Co., Ltd., fluorine-based water repellent, solid content 20%) Paracat PGW 18 g / liter (Ohara Palladium Chemical Co., Ltd., block isocyanate crosslinking agent) Sumi Tex Resin M-3 3 g / l (melamine cross-linking agent, manufactured by Sumitomo Chemical Co., Ltd.) Sumitex Accelerator ACX 3 g / l (cross-linking accelerator, manufactured by Sumitomo Chemical Co., Ltd.) Isopropyl alcohol 30 g / l

Comparative Example 5 Next, as a comparative example of the present invention, a nylon fabric of Comparative Example 5 was obtained by processing in exactly the same processing method as in the present invention 3 except that the acid treatment was omitted. Examples 3 and 4 and Comparative Examples 3, 4, and 5
The performance of the processed fabric was measured and evaluated, and the results are shown in Table 2.

[0032]

[Table 2]

As is clear from Table 2, the processed fabrics of Examples 3 and 4 have a water repellency of 80 points or more and a friction band voltage of 2000 V or less even after 10 times of washing, and have excellent washing durability. It can be seen that it has both antistatic properties and antistatic properties. On the other hand, the processed fabric of Comparative Example 3 has insufficient water repellency after 10 washings, the processed fabric of Comparative Example 4 has insufficient antistatic properties after 10 washings, and the processed fabric of Comparative Example 5 has 10 washings. Both the water repellency and antistatic properties were insufficient.

[0034]

According to the method of the present invention, it is possible to simultaneously impart water repellency and antistatic performance having washing durability to a nylon fabric, and to provide a windbreaker, ski wear,
It can be widely used for sports clothing such as fishing wear, work clothes, uniforms such as uniforms, and general clothing.

Claims (1)

[Claims] 1. A first method, wherein an electrostatic treatment agent comprising an addition polymer of an alkylene oxide-containing polyol and an isocyanate is applied in an amount of 0.5 to 1% by weight to a nylon fiber fabric.
A second step of treating the fabric in an acidic aqueous solution, and adding a water-repellent treating agent comprising a copolymer with a perfluoroalkyl group-containing acrylate or methacrylate or a compound copolymerizable thereto to the fabric. A durable antistatic / water-repellent processing method for a nylon-based fiber cloth, which comprises a third step of providing a water-repellent water-repellent material.