JPH1136176A - Antistatic and water repellent fabric and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject fabric having antistatic and water repellent performances both excellent in washing durability by reacting a nylon fiber with a specific antistatic resin compound, treating the product with low- temperature plasma and then coating it with a water repellent resin. SOLUTION: This fabric is obtained by forming an antistatic resinous layer on the fiber surface of a synthetic fiber fabric made mainly of a nylon fiber, the resin compound in the resinous layer having two or more functional groups reactive with any amino end group of the nylon fiber in a molecule, having a molecular weight of >=100 and an antistatic property of <=1200, and being built up in a quantity of 1-5 wt.% based on the fabric weight, followed by heating treatment to react itself with the nylon fiber, treating the layered fiber with low-temperature plasma and further coating the layered fiber with a water repellent resin, which consists of three components of (A) a perfluoroalkyl group-containing (meth)acrylate or a copolymer having it as a structuring unit, (B) a triazine compound and (C) a blocked isocyanate compound, to obtain the objective fabric excellent also in NOx fastness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic fiber cloth mainly composed of nylon fibers having excellent antistatic and water repellent properties having excellent washing durability and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, synthetic fiber fabrics tend to accumulate static electricity, and this tendency is particularly remarkable for nylon fiber fabrics. For this reason, there has been a problem that static electricity is generated when sewing or wearing a sewn product, causing discomfort due to electric shock or clinging to a body, and easily adsorbing dust in the air and becoming dirty. In addition, these fabrics are often used for outer garments, but there is also a problem that clothes get wet due to rain or snow.

Conventionally, various methods have been proposed to address the above-mentioned problems. Regarding antistatic processing, there is a method of forming a complex on the fiber surface by treating with an ionic polymer activator,
A method in which a mixture of basic and amide-based low-molecular substances is applied to the fiber and grafted to the fiber surface by dry heat, wet heat, radiation, microwaves, ultraviolet rays, etc., and also contains a block polymer of ethylene glycol and propylene glycol And a polymerizable monomer composed of acrylic or methacrylic terminals, a prepolymer containing a block polymer of ethylene glycol and propylene glycol, and having a crosslinkable functional group at the terminal, alone or in combination with a crosslinking agent. Methods for resinification have been proposed.

[0004] On the other hand, the water repellent treatment is usually carried out by impregnating a fabric with a water repellent such as a fluorine water repellant or a silicon water repellent in a final finishing step, and then performing a dry heat treatment. In particular, many water repellent treatments using a fluorine-based water repellent which is excellent in washing durability are performed. In addition, there are many processing methods for simultaneously imparting antistatic properties and water repellency to synthetic fiber cloths. Generally, in the final finishing step, an alkylsulfonic acid type or alkylphosphoric acid is used as a fluorine-based water repellent. It is processed by a method in which an ester type antistatic agent is mixed and impregnated by a padding method. However, although the antistatic water-repellent cloth obtained by the above method is excellent in general performance, it has a drawback that the performance for washing is greatly reduced. There is a problem that it is easily wetted by snow and dust easily adheres due to generation of static electricity.

[0005] In response to these requirements, in the case of polyester materials, a treatment liquid containing a polyethylene glycol resin and a water-soluble polyester resin is applied to polyester fibers, as typified by JP-A-6-158534, and dried. , Treated with low-temperature plasma of non-polymerizable gas,
Then, there is a known processing technique of performing a water-repellent processing. By the way, in recent years, due to the prosperity of outdoor sports, a demand for a durable antistatic water-repellent cloth using a lightweight synthetic fiber cloth mainly made of a nylon material is increasing more and more. However, as described above, it is difficult to impart durability and anti-water repellency to nylon materials compared to polyester materials, and it is very difficult to achieve both of these functions. Technology. Further, nylon fibers are liable to discolor when exposed to the atmosphere or exposed to ultraviolet light for a long time, and the phenomenon is particularly remarkable in the case of white or light-colored systems, so that it is the present situation. The present invention has been made in view of the above situation, and has been made to manufacture a synthetic fiber cloth mainly composed of nylon fibers having excellent antistatic performance and water repellency having excellent washing durability and excellent NOx fastness. It is intended to do so.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve such problems, and as a result, have at least two or more functional groups in the molecule capable of reacting with the amino terminal contained in the nylon fiber. After reacting an antistatic resin compound and nylon fiber on the fiber surface, the surface is subjected to low-temperature plasma treatment, and a water-repellent resin layer is formed on the surface to provide a highly durable resin. The inventors have found that an electro-repellent synthetic fiber fabric can be obtained, and have reached the present invention.

That is, the present invention relates to "1. Synthetic fiber cloth mainly composed of nylon fiber, in which a resin layer having antistatic properties is formed on the fiber surface, and a resin layer having water repellency is formed thereon. The fabric is characterized by having a water repellency of 80 points or more after 20 home washings, a friction band voltage of 1000 V or less, a half-life of 10 seconds or less, and a NOx fastness of class 4 or more. An anti-static water-repellent fabric that has at least two functional groups capable of reacting with the amino terminal contained in the nylon fiber and has a molecular weight of 100 or more and 1
After adhering 1 to 5% by weight of a resin compound having an antistatic property of 200 or less to the fiber cloth, the surface thereof is subjected to a low-temperature plasma treatment, and then (1) a perfluoroalkyl group-containing acrylate, methacrylate or the like. 1 to 10% by weight, 0.01 to 1% by weight, based on the fiber cloth, of a copolymer with a compound which can be copolymerized with (3) a (2) triazine compound and (3) a blocked isocyanate compound.
Wt.%, 0.01 to 1% by weight of the fabric. "

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
As used herein, the term “fiber cloth composed of synthetic fibers mainly composed of nylon fibers” refers to nylon 6, nylon 66, nylon 46, nylon 61 generally called polyamide fibers.
Synthetic fiber woven fabric, knitted fabric and non-woven fabric containing 50% or more of fibers such as 0, nylon 11, nylon 12, etc.

In the present invention, the above-mentioned fiber cloth has at least two functional groups capable of reacting with the amino terminal in the nylon fiber in the molecule and has a molecular weight of 100 or more and 120 or more.
1 to 5% by weight of a resin compound having an antistatic property of 0 or less is applied. Examples of the resin compound having at least two functional groups capable of reacting with the amino terminal contained in the nylon fiber used in the molecule and having a molecular weight of 100 or more and 1200 or less include polyethylene. Glycol diglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like can be mentioned, and polyethylene glycol diglycidyl ether is particularly preferably used. Those having a molecular weight of 100 to 1200 can be used for these resin compounds.
If the molecular weight is out of this range, the fiber cannot be provided with antistatic properties having sufficient durability against repeated washing.

In the present invention, an aqueous solution of the above-described resin compound having antistatic properties is applied to a synthetic fiber fabric, and is applied in a solid content of 1 to 5% by weight based on the fiber weight. Here, if the adhesion amount is less than 1% by weight, sufficient antistatic performance cannot be obtained, and if it exceeds 5% by weight, the feeling is extremely hardened, which is not preferable. In order to apply this aqueous solution to the synthetic fiber cloth, the fiber cloth may be immersed in a treatment bath and then uniformly squeezed with a mangle, and the method is not particularly limited in the present invention. In the present invention, drying and heat treatment are performed on the synthetic fiber cloth to which the above-described resin compound has been added. Drying may be performed by a usual method, and is not particularly limited in the present invention. The subsequent heat treatment is performed at 150 to 170 ° C. for 30 to 90 seconds. If the heat treatment temperature is lower than 150 ° C., sufficient durability and antistatic properties cannot be obtained, and if it is higher than 170 ° C., the fiber cloth is hardened, which is not preferable.

Next, in the present invention, the synthetic fiber cloth is subjected to a low-temperature plasma treatment. For the generation of low-temperature plasma, the pressure of the closed container containing the fiber cloth is reduced by a vacuum pump, and a gas for processing is introduced into the container. The type of gas to be introduced may be any non-polymerizable gas that does not cause plasma polymerization, such as inert gas, oxygen, nitrogen, and air. In particular, air and oxygen gas are preferably used in consideration of economic efficiency. . In addition, the pressure of the gas to be introduced must be adjusted in the range of 0.2 to 2 Torr. If the pressure is out of the range, low-temperature plasma does not occur and the characteristics of the fabric of the present invention cannot be obtained. The generation of plasma used in the present invention can be obtained by applying electric energy to the above-mentioned atmosphere to cause glow discharge. At this time, as an electric energy source,
Although either a DC voltage or an AC voltage (1 KHz to 3 GHz) may be used, 13.56 MHz is generally used from the viewpoint of the stability and uniformity of plasma generation and the regulations of the Radio Law. The output is
The target performance of the present invention can be obtained with 0.1 to 1 W / cm ² and processing time of 10 to 180 seconds.

Thereafter, in the present invention, (1) a copolymer with a perfluoroalkyl group-containing acrylate or methacrylate or a compound copolymerizable therewith; (2) a triazine compound; and (3) a blocked isocyanate compound.
The cloth is impregnated with a water-repellent treatment liquid comprising the above components, and the solid content is 1 to 10% by weight, 0.01 to
1% by weight, 0.01 to 1% by weight. The perfluoroalkyl group-containing acrylate and methacrylate referred to herein are compounds represented by the following general formula 1 and impart water repellency to fibers.

[0013]

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(Where R ₁ is hydrogen or a lower alkyl group, R _f is a perfluoroalkyl group represented by C _m F _{2m + 1} (where m is an integer of 2 to 21), and n is 10 to 200 The compound copolymerizable with the compound represented by the above general formula includes vinyl compounds such as acrylic acid, methacrylic acid, styrene, and vinyl chloride. Perfluoroalkyl group-containing acrylates, methacrylates, or copolymers with these copolymerizable compounds,
It is preferably in the range of 1 to 10% by weight based on the weight of the fabric. Here, if the adhesion amount is less than 1% by weight, it is difficult to obtain the durable water repellency intended in the present invention, which is not preferable.
On the other hand, if the amount exceeds 10% by weight, not only is the durability of the present invention not only saturated but also the feeling becomes hard, which is not preferable.

The triazine compound used in the present invention is a compound represented by the following general formula (2), which is a compound of the above-mentioned perfluoroalkyl group-containing acrylate or methacrylate or a copolymer with a compound copolymerizable therewith. This is to improve the adhesion to the fiber.

[0016]

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(However, R ₁ to R ₆ are all -H,
_{-OH, -CH 2 OCH 3, -CH} 2 OC 2 H 5, -C
_{H 2 OH, -CH 2 CH 2} OH or -CH ₂ CH ₂ CH
₂ OH. Among the compounds represented by the above general formula, particularly, trimethylolmelamine, hexamethylolmelamine and the like are preferably used. It is preferable that the adhesion amount of such a triazine compound is in the range of 0.01 to 1% by weight based on the weight of the fabric. If the amount of adhesion is less than 0.01% by weight, it is difficult to obtain the desired durable water repellency in the present invention. If the amount of adhesion exceeds 1% by weight, the durable water repellency not only reaches saturation but also increases It is not preferable because the combination becomes hard.

The blocked isocyanate compound used in the present invention may be any compound as long as the isocyanate group is generally blocked with ketoxime, phenol, caprolactam, etc., and the block is released by a suitable heat treatment, and a free isocyanate group appears. Improve the strength of the water-repellent resin film by cross-linking copolymers of alkyl group-containing acrylates, methacrylates or compounds copolymerizable with them, or cross-linking this copolymer with triazine compounds. Things. It is preferable that the adhesion amount of such a blocked isocyanate compound is in the range of 0.01 to 1% by weight based on the weight of the fabric. If the amount of adhesion is less than 0.01% by weight, it is difficult to obtain the durability and water repellency intended in the present invention. If the amount of adhesion exceeds 1% by weight, the durability and water repellency not only reach saturation but also increase the feeling. Is not preferred because it becomes hard.

Methods for imparting these water-repellent resins to fiber fabrics include the above-mentioned perfluoroalkyl group-containing acrylates, methacrylates or copolymers with compounds copolymerizable therewith, triazine compounds, catalysts for triazine compounds, The block isocyanate compound and the catalyst of the blocked isocyanate compound are used as a mixed treatment liquid such as an emulsion, an organic solvent solution, and an aqueous solution, and applied to the fiber cloth by using a known pad method, a spray method, or the like. Thereafter, the synthetic fiber fabric is dried and heat-treated. Drying may be performed by a usual method, and is not particularly limited in the present invention. Subsequent heat treatment is carried out at 160-180 ° C, more preferably 170
Perform at ~ 180 ° C. If the heat treatment temperature is lower than 160 ° C,
If sufficient durability and antistatic property cannot be obtained, and if the temperature is higher than 180 ° C., the fiber cloth is hardened, which is not preferable.

[0020]

[Function] When a resin compound having an antistatic property having at least two functional groups capable of reacting with the amino terminal contained in the nylon fiber in the molecule reacts with the amino terminal in the nylon fiber, a strong antistatic effect is produced on the surface of the fiber. When a conductive film is formed and plasma treatment is applied thereon, the fiber surface is further hydrophilized to improve antistatic properties, and at the same time, a large number of reactive functional groups are generated on the fiber surface. Therefore, it is strongly bonded to the durable water-repellent resin film to be applied thereafter, and antistatic water-repellent performance with washing durability can be obtained. On the other hand, NOx
The reason for the improvement in the fastness is that the amino terminal, which is highly reactive and contributes to the discoloration of the nylon fiber, has at least two functional groups in the molecule that can react with the amino terminal used in the present invention. It is speculated that by reacting with an electrically conductive resin, the amino terminus of the fiber is blocked, thereby suppressing discoloration.

[0021]

Next, the present invention will be described more specifically.
Regarding the antistatic property and water repellency of the fabric in the examples,
After processing and home washing (JISL-1027,10
3 Method) For the sample after 20 times, and for the NOx fastness, the sample after processing was measured and evaluated by the following method. (1) Antistatic property Friction band voltage JISL-1094 B method Half life JISL-1094 A method (2) Water repellency JISL-1092 Spray method (3) NOx fastness JISL-0855

EXAMPLE 1 A woven fabric (warp density: 150 yarns / inch, weft density: 70 yarns / inch) using a nylon bulky yarn 70 denier / 34 filaments as a warp and nylon processed yarns 155 denier / 96 filaments as a weft. ), After normal scouring and drying,
Dyeing was performed under the conditions of 85 ° C. for 30 minutes in the following prescription 1, followed by ordinary drying to obtain a light blue dyed cloth. Formulation 1 Tectilon Blue 4R 0.05% owf (manufactured by Ciba Geigy, acid dye) Leveran NKD 2% owf (manufactured by Marubishi Yuka Co., leveling agent) Acetic acid (48% concentration) 0.2 g / liter

Next, an aqueous solution represented by the following formula 2 is prepared, the dyed cloth is immersed in the solution, squeezed uniformly with a mangle at a squeezing ratio of 70%, and dried at a temperature of 110 ° C. for a time of 60 seconds. Subsequently, heat treatment was performed at a temperature of 160 ° C. for a time of 90 seconds. Formulation 2 polyethylene glycol diglycidyl ether 3% by weight (polyethylene glycol molecular weight 880)

This fabric was subjected to low-temperature plasma processing under the following low-temperature plasma processing conditions. Low-temperature plasma processing conditions Gas used Oxygen pressure 1 Torr High frequency 13.56 MHz High frequency output 0.6 W / cm ² Processing time 60 seconds

Next, the fabric after the low-temperature plasma treatment was immersed in a water-repellent treatment solution shown in Formula 3 below, and was uniformly squeezed with a mangle at a squeezing ratio of 60%. Then, heat treatment was performed under the conditions of a temperature of 170 ° C. and a time of 60 seconds to obtain a processed fabric of the present invention. Formulation 3 Asahigard LS-317 10% by weight (manufactured by Meisei Chemical Co., Ltd., organic fluorine-containing compound water / oil repellent) Sumitex Resin M-3 0.3% by weight (Sumitomo Chemical Co., Ltd., trimethylolmelamine Sumitex Accelerator ACX 0.3% by weight (Sumitomo Chemical Co., Ltd., catalyst for trimethylol melamine) BP-10M 0.1% by weight (Meisei Chemical Co., Ltd., aliphatic block isocyanate) V-2 0.1% by weight (Catalyst for aliphatic block isocyanate manufactured by Meisei Chemical Industry Co., Ltd.)

For the purpose of comparison with the present invention, the following formulation 4 and formulation 5 were used in place of formulation 2 in this example.
Two antistatic and water-repellent cloths for comparison were produced by exactly the same method as in the present example (comparative examples 1 and 2 respectively).
I got Formulation 4 Polyethylene glycol diglycidyl ether 0.3% by weight (polyethylene glycol molecular weight 880) Formulation 5 Polyethylene glycol diglycidyl ether 3% by weight (polyethylene glycol molecular weight 2200)

Further, for comparison with the present invention, except for omitting the plasma treatment in this example, the antistatic water-repellent cloth for comparison was used in exactly the same manner as in this example (Comparative Example 3).
I got Furthermore, for comparison with the present invention, two antistatic water-repellent cloths for comparison were prepared in exactly the same manner as in this example except that the following formulations 6 and 7 were used instead of formulation 3 in this example. Comparative Examples 4 and 5) were obtained. Formulation 6 Asahigard LS-317 10% by weight Formulation 7 Asahigard LS-317 5% by weight Sumitex Resin M-3 0.3% by weight Sumitex Accelerator ACX 0.3% by weight BP-10M 0.1% by weight Pass Axel V-2 0.1% by weight

The performances of the present invention and the work cloth for comparison were measured and evaluated, and the results are shown in Table 1.

[0029]

[Table 1]

As apparent from Table 1, the processed fabric of the present invention has both excellent antistatic properties and water repellency after 20 washes as well as the initial stage, and has good NOx fastness. I understand.

[0031]

According to the present invention, it is possible to obtain a synthetic fiber cloth having excellent antistatic and water repellent properties and excellent NOx fastness with excellent washing durability. Due to its performance, the durable antistatic water-repellent fabric of the present invention can be used for sports clothing such as windbreakers, ski wear, fishing wear, and uniforms such as work clothes.

Claims (2)

[Claims] 1. A cloth comprising a synthetic fiber cloth mainly composed of nylon fibers, wherein a resin layer having antistatic properties is formed on the fiber surface, and a water-repellent resin layer is formed thereon. After 20 cycles, the water repellency was 80 points or more, the friction band voltage was 1000 V or less, the half-life was 10 seconds or less, and NO
An anti-static water-repellent cloth characterized by having an x-fastness of class 4 or higher. 2. An antistatic resin compound having at least two functional groups capable of reacting with an amino terminal contained in a nylon fiber in a molecule and having a molecular weight of 100 or more and 1200 or less is added to a fiber cloth. 1-5% by weight, and then subjected to low-temperature plasma treatment on the surface, and thereafter (1) a copolymer with a perfluoroalkyl group-containing acrylate or methacrylate or a compound copolymerizable therewith, (2) Three components of a triazine compound and (3) a blocked isocyanate compound are each added to a fiber fabric in an amount of 1
A method for producing an antistatic and water-repellent fabric, characterized in that the fabric is adhered to the fabric by 10 to 10% by weight, 0.01 to 1% by weight, 0.01 to 1% by weight.