JP3401596B2 - Method for modifying one side of fabric and fabric having one side modified - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying one side of a woven or knitted fabric or a non-woven fabric and a woven or knitted fabric or a non-woven fabric whose one side is modified.

[0002]

2. Description of the Related Art Water is constantly evaporating from human skin in normal times due to body temperature regulation and physiological sweating function. However, when performing intense sports, the amount of sweating is kept in order to prevent a sudden rise in body temperature. Increase.

Therefore, during intense sports, the humidity in the space inside the clothes also rises, and when the temperature reaches 33 ° C. and the humidity exceeds 65%, the sweat that reaches the body surface from the sweat line cannot be gasified, and liquid-phase sweating begins. It is being appreciated.

Originally, an increase in the amount of perspiration has the function of lowering the body temperature which rises due to heat of vaporization, but if sweat remains on the skin surface or is retained on the clothing surface in contact with the skin, it will be caused by the heat of vaporization. Body temperature regulation will not work effectively,
The temperature inside the clothes and the amount of sweating increase more and more.

On the other hand, when sweat is present on the body surface or on the clothing surface in contact with the skin when the body temperature begins to drop after the exercise, these are vaporized and cause a feeling of coldness.

<Sweatiness> during or after such exercise
In order to eliminate discomfort such as <greasy feeling> and <cool feeling>, it is necessary to have clothes having physical properties capable of promptly absorbing sweat on the body surface and promptly releasing it from the part in contact with the skin to the external environment.

When the conventional fiber materials are evaluated from this point of view, the fiber material made of 100% natural fibers such as cotton and wool has excellent water absorption and thus absorbs perspiration well. The absorbed sweat does not easily evaporate, a considerable amount of water remains inside the fiber, and it takes time to dry. On the other hand, a fiber material made of 100% synthetic fibers has a low water absorption rate when it comes into contact with water and is inferior in water permeability, so that it does not absorb or move sweat, which causes discomfort due to wetting with sweat.

[0008] Even in the case of a blended product of natural fibers and synthetic fibers, the absorbed sweat is absorbed by the natural fibers and is in a water-containing protected state, so that sweat (moisture) is not easily evaporated.

In order to solve these drawbacks, a cloth has been proposed in which one side is hydrophobic and the other side is hydrophilic.

Here, FIG. 1 shows a model diagram of water absorption and water permeability of a hydrophobic woven / knitted fabric, a hydrophilic woven / knitted fabric on both sides and a woven / knitted fabric on one side of which is hydrophobic and the other side is hydrophilic. .

In a hydrophobic woven or knitted fabric such as a fiber material made of 100% synthetic fibers, the moisture permeation layer does not reach the outside as shown in the model diagram (A) of FIG. In a woven or knitted fabric with hydrophilic properties on both sides, such as a fiber material made of 100% natural fiber, the moisture permeation layer reaches the outside as shown in the model diagram (B), but the inner and outer moisture permeation layers are evenly spread. . In the woven or knitted fabric having both the hydrophilic surface and the hydrophobic surface, as shown in (C), the water permeation layer on the hydrophilic surface expands as compared with the water permeation layer on the hydrophobic surface.

That is, the behavior that is really required for sweat in a woven or knitted fabric such as sports clothing or underwear is not that the sweat is hydrated inside the woven or knitted fabric, but rather that the sweat side is not hydrated inside the woven or knitted fabric. It is to move from the hydrophobic surface in contact with to the hydrophilic surface which is always in contact with the outside air, and to diffuse and disperse sweat on the surface layer. That is, a woven or knitted fabric with one side being hydrophobic and the other side being hydrophilic can achieve such behavior.

Accordingly, various methods have been proposed for obtaining a woven or knitted fabric having one side having a hydrophobic side and the other side having a hydrophilic side. For example, one side of the woven or knitted fabric has a hydrophilic drug or a water repellent property. It is known that a post-processing method of applying a chemical can easily produce a woven or knitted fabric that does not cause a feeling of dampness, stickiness, and the like. However, a woven or knitted fabric obtained by such a processing method has poor wash resistance because it is simply coated with a chemical, and has poor breathability because the coated chemical causes clogging of the woven or knitted fabric.

A method has also been proposed in which one side of a synthetic fiber woven or knitted fabric is subjected to a low temperature plasma treatment under reduced pressure to impart hydrophilicity to obtain a woven or knitted fabric having different functions on the front and back sides by utilizing the low temperature plasma method. . In the processing method, a synthetic fiber woven / knitted fabric is fixed on the electrode surface in an internal electrode type plasma device using parallel plate type electrodes to treat one side of the woven / knitted fabric, but the woven / knitted fabric has air permeability. Therefore, when plasma irradiation is performed, the entire woven or knitted fabric (both front and back surfaces) is plasma-treated. Therefore, even with such a method, sufficient front and back different functions have not been obtained.

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for treating a woven or knitted fabric or a non-woven fabric which does not have such a defect and a woven or knitted fabric or a non-woven fabric which does not have such a defect.

[0016]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the above object by irradiating one side of a woven or knitted fabric or a non-woven fabric with plasma generated between atmospheric pressure plasma generating electrodes. I found that I can do it. The present invention has been completed based on these findings.

That is, the present invention provides the invention according to the following items.

Item 1 Plasma generated between the atmospheric pressure plasma generating electrodes is irradiated to one side of a woven or knitted fabric or a non-woven fabric arranged outside the electrodes to generate active species, and then the active species is charged with a polymerizable monomer. A method for modifying one side of a woven or knitted fabric or a non-woven fabric to be graft-polymerized.

Item 2. The method according to Item 1, wherein the polymerizable monomer is sprayed onto one side of the woven or knitted fabric or the nonwoven fabric when the polymerizable monomer is graft-polymerized to the active species.

Item 3 A hydrophobic woven or knitted or non-woven fabric obtained by graft-polymerizing a hydrophilic monomer on one side, which comprises JIS L 1
A woven or knitted fabric or nonwoven fabric having a water absorption rate of 3 seconds or less on one side and 100 seconds or more on the other side according to the method 096A.

Item 4 A hydrophobic woven or knitted fabric obtained by graft-polymerizing a hydrophilic monomer on one side, wherein the number of hydrophilic groups on one side is 3 times or more the number of hydrophilic groups on the other side. A woven or knitted fabric or a non-woven fabric.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

Method of the Present Invention In the method of the present invention, as a first step, plasma generated between the atmospheric pressure plasma generating electrodes is applied to one surface of the woven or knitted fabric or the nonwoven fabric to activate the surface of the woven or knitted fabric or the nonwoven fabric. In the second step, the polymerizable monomer is graft-polymerized on the surface of the woven or knitted fabric or the nonwoven fabric by utilizing the polymerizable active species on the surface of the woven or knitted fabric or the nonwoven fabric activated by irradiation with plasma.

[First Stage] In the first stage, the woven or knitted fabric or the nonwoven fabric is subjected to plasma treatment. (1) Type of material The woven or knitted fabric or nonwoven fabric (hereinafter, "woven or knitted fabric or nonwoven fabric" may be referred to as "fabric") used in the present invention may be hydrophilic or hydrophobic. Hydrophobic fibers are preferred.

As the hydrophobic fiber, polyester fiber,
Various fibers such as polyamide-based, polypropylene-based, and polyacrylic-based synthetic fibers can be exemplified.

Examples of hydrophilic fibers include cotton, hemp, silk and wool.

As the woven or knitted fabric or the non-woven fabric, a woven or knitted fabric or non-woven fabric which is a mixed spinning of hydrophobic fibers and hydrophilic fibers can be used. An example of such a woven or knitted fabric or a nonwoven fabric is a mixed spinning of polyester fiber and cotton.

The basis weight of the woven or knitted fabric or the nonwoven fabric is not particularly limited, but is usually about 30 to 500 g / m ² .

The thickness of the woven or knitted fabric or nonwoven fabric used in the present invention is not particularly limited, and may be a relatively thin woven or knitted fabric or nonwoven fabric. The thickness of the woven or knitted fabric or the nonwoven fabric is usually about 50 to 1,000 μm. According to the method of the present invention, even a relatively thin woven or knitted fabric or a non-woven fabric (about 100 μm or less) can have different functions on the front and back sides.

Although the thickness of the fiber is not particularly limited, it is usually about 15 to 400 denier. (2) Plasma treatment The plasma treatment in the method of the present invention can be carried out by irradiating the plasma generated between the atmospheric pressure plasma generating electrodes with one surface of the woven or knitted fabric or the non-woven fabric arranged outside the plasma generating electrodes. .

In the method of the present invention using the atmospheric pressure plasma generator, the plasma is generated in the absence of the woven or knitted fabric or the nonwoven fabric, and the plasma (active species generated by the plasma) is applied to one side of the woven or knitted fabric or the nonwoven fabric. It is different from the conventional method in which plasma treatment is performed by generating plasma in the presence of a woven or knitted fabric or a nonwoven fabric.

Plasma is generated between the atmospheric pressure plasma electrodes by a discharge generating electrode and a counter electrode (ground potential) configured to generate plasma by discharge under atmospheric pressure.
It can be performed using an atmospheric pressure plasma generator equipped with.

In the atmospheric pressure plasma generator, for example, a discharge generating electrode and a counter electrode are present with a discharge space for introducing a gas separated from each other, and a high frequency power source for applying a high frequency voltage to the discharge generating electrode is provided. The discharge generating electrode may be provided with a high frequency voltage to generate plasma in the discharge space, and the plasma may be irradiated to the surface of the object to be treated (woven or knitted fabric or nonwoven fabric). it can.

It is preferable to use the atmospheric pressure plasma generator because it is not necessary to evacuate the inside of the apparatus, so that no process or equipment for it is required and continuous processing can be easily performed. If the plasma treatment can be continuously performed, it is possible to easily treat the treatment object regardless of the size (length) of the treatment object (woven or knitted fabric or non-woven fabric) even if the plasma generator is small. It is preferable because it can be performed efficiently.

Therefore, the plasma treatment in the method of the present invention may be continuously performed. Such continuous plasma processing method can be performed, for example, as schematically shown in FIG. Alternatively, for example, the method described in Japanese Patent No. 2893259 may be used.

As the atmospheric pressure plasma generator,
A blow-out type atmospheric pressure plasma generator can be used. The blowout-type atmospheric pressure plasma generator is, for example, in the atmospheric pressure plasma generator having the above-mentioned configuration,
A counter electrode surrounds the discharge generating electrode and is formed in a cylindrical shape having a nozzle-shaped outlet. As such a blow-out type atmospheric pressure plasma generator, Japanese Patent Laid-Open No. 10-19969
A blow-out type atmospheric pressure plasma generator as described in JP-A-7 can be preferably used. The schematic diagram is shown in FIG.

The conditions of the plasma treatment using the atmospheric pressure plasma generator are not particularly limited and can be appropriately set according to the type (material, thickness, density, etc.) of the woven or knitted fabric or the nonwoven fabric.

The gas used to generate plasma (gas supplied to the discharge space between the plasma generating electrodes) is helium gas, or helium gas and oxygen gas, argon gas, nitrogen gas, hydrogen gas, carbon dioxide, etc. A mixed gas may be used. It is preferable to use helium gas or a mixed gas of helium gas and another gas because stable glow discharge plasma is easily generated. When using a mixed gas of helium gas and other gases, use helium gas, for example, 50 vo
It is preferably about 1% or more.

From the viewpoint of discharge sustainability and plasma uniformity, it is preferable to use, for example, about 100 W to 2 kW (frequency of about 100 kHz to 500 MHz) as the input power.

The gas pressure during discharge is approximately atmospheric pressure.

The flow rate of the gas is not particularly limited and can be set appropriately, but is usually about 10 L / min or less. The lower limit of the gas flow rate is not particularly limited, but is about 0.1 L / min.

The method of irradiating the woven or knitted fabric or the non-woven fabric with the plasma generated in the plasma generator is not particularly limited, but for example, an outlet (blow-out port) configured in a nozzle shape.
From about 1 mm to 10 cm, preferably 3 to 10 mm
It is possible to irradiate a woven or knitted fabric or a non-woven fabric placed at some distance.

The feeding speed of the woven or knitted fabric or the nonwoven fabric in the case of continuous treatment can be appropriately set according to the type of the woven or knitted fabric or the nonwoven fabric, the flow rate of gas, the high frequency power, etc. About 100, preferably 100
It is about 0 mm / min or less.

The plasma may be applied to the entire surface of the woven or knitted fabric or the non-woven fabric, but if it is partially irradiated, sweat can be removed more smoothly, and it is particularly suitable for use in underwear. .

The plasma treatment produces active species on the surface of the woven or knitted fabric or the nonwoven fabric.

[Second Stage] In the second stage, the surface of the woven or knitted fabric or nonwoven fabric containing the active species obtained in the first stage is brought into contact with a radical-polymerizable monomer for graft polymerization.

The contact between the surface of the woven or knitted fabric or the non-woven fabric having the active species and the monomer may be carried out under atmospheric pressure, or the surface of the woven or knitted fabric or the non-woven fabric may be preliminarily set to, for example, about 0.1 Torr or less (13.3 Pa). It may be carried out after vacuum deaeration to about the following). Vacuum deaeration in advance removes the air contained in the woven or knitted fabric or the nonwoven fabric, and the graft polymerization reaction proceeds more easily, which is preferable. It is also possible to perform vacuum deaeration while bringing the woven or knitted fabric or the nonwoven fabric into contact with the monomer.

In the method of the present invention, the graft polymerization reaction on one side of the woven or knitted fabric or the nonwoven fabric can be carried out by a commonly used method, for example, by a gas phase reaction or a liquid phase reaction (immersion method or impregnation method). You can go. When the graft polymerization reaction is carried out in the gas phase, the production of the homopolymer is suppressed as compared with the liquid phase reaction, the amount of the graft polymer is easily controlled, and the texture of the woven or knitted fabric or the nonwoven fabric is unlikely to deteriorate. . Therefore, it is desirable to carry out the graft polymerization by a gas phase reaction.

The graft polymerization reaction can be carried out by spraying a polymerizable monomer onto a woven or knitted fabric or a nonwoven fabric (impregnation method). When the graft polymerization reaction is carried out by the impregnation method,
The durability of the obtained cloth having different front and back functions is particularly excellent.

The conditions for the graft polymerization reaction can be appropriately set depending on the kind of the monomer and the like, and are not particularly limited as long as a desired graft polymerization amount (hydrophilic or hydrophobic) can be obtained. In the case of the vapor phase method or the immersion method,
The temperature is about 15 to 80 ° C. and the time is about 10 minutes to 30 hours.

The impregnation method can be carried out, for example, by spraying the polymerizable monomer on the plasma-irradiated surface of the cloth together with an inert gas such as nitrogen while continuously moving the cloth. When spraying, an undiluted solution of the monomer (100% of the monomer) may be used, or an aqueous solution may be used. In the impregnation method, a heating step may be provided or a heating step may not be provided. The heating may be performed while spraying, or may be performed after spraying, usually,
It is carried out at about 30 to 90 ° C. for about 10 minutes to 30 hours, preferably about 1 to 25 hours. When the heating step is not provided, it may be left for about 1 to 30 hours after spraying.

The radical-polymerizable monomer used in the present invention can be appropriately selected depending on the use of the woven or knitted fabric or the nonwoven fabric. When the woven or knitted fabric or the nonwoven fabric is hydrophobic, a hydrophilic monomer is used. When a woven or knitted fabric or a non-woven fabric is hydrophilic, a hydrophobic monomer is used. When the woven or knitted fabric or the non-woven fabric is a blend of hydrophobic and hydrophilic fibers, hydrophilic or hydrophobic monomers can be appropriately selected and used.

Here, the radically polymerizable monomer is
It is a monomer which has a carbon-carbon double bond and whose polymerization reaction proceeds by chain polymerization.

Examples of hydrophilic monomers include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-vinyl-2-pyrrolidone, and acrylic acid-2- ( Examples include N, N-dimethylamino) ethyl, 2- (N, N-dimethylamino) ethyl methacrylate, 4-vinylpyridine, 2-vinylpyridine and the like.

Examples of the hydrophobic monomer include perfluorooctylethyl acrylate and perfluorooctylethyl methacrylate.

The combination of the woven or knitted or non-woven fabric and the radical-polymerizable monomer can be appropriately selected according to the purpose of use, but in particular, the combination of the following woven or knitted or non-woven fabric and the monomer was obtained. A woven or knitted fabric or a non-woven fabric is preferable because it has an excellent function of transferring moisture from one surface of the woven or knitted fabric or the non-woven fabric to the other surface.

As the combination of the hydrophobic woven or knitted fabric or nonwoven fabric and the hydrophilic monomer, polyester-based woven or knitted fabric or nonwoven fabric and acrylic acid, polyester-based woven or knitted fabric or nonwoven fabric and methacrylic acid, polyester-based woven or knitted fabric or nonwoven fabric and acrylic acid can be used. 2-Hydroxyethyl, polyester-based woven or knitted fabric and 2-hydroxyethyl methacrylate, polyester-based woven or knitted fabric and N-vinyl-2-pyrrolidone, polyamide-based woven or knitted fabric and acrylic acid, polyamide-based woven or knitted fabric Or non-woven fabric and methacrylic acid, polyamide woven or knitted fabric or non-woven fabric and 2-hydroxyethyl acrylate, polyamide woven or knitted fabric or non-woven fabric and methacrylic acid-
2-hydroxyethyl, polyamide plain weave or non-woven fabric and N-vinyl-2-pyrrolidone, polypropylene woven knitted fabric or non-woven fabric and acrylic acid, polypropylene plain weave or non-woven fabric and methacrylic acid, polypropylene based plain weave or non-woven fabric and acrylic acid-2-hydroxy Ethyl, polypropylene plain weave or nonwoven fabric and 2-hydroxyethyl methacrylate, polypropylene plain weave or nonwoven fabric and N-vinyl-2
A combination of-pyrrolidone is preferred. Among these combinations, a combination of polyester woven or knitted fabric or nonwoven fabric and acrylic acid is particularly preferable.

The hydrophilic woven or knitted fabric or non-woven fabric and the hydrophobic monomer may be used in combination with a cotton-based woven or knitted fabric or non-woven fabric with perfluorooctylethyl acrylate or a cotton-based woven or knitted fabric or non-woven fabric with perfluorooctylethyl methacrylate. Is preferred.

The amount of the monomer used can be appropriately selected depending on the reaction conditions and the like, and is particularly limited as long as it is an amount capable of imparting hydrophilicity or hydrophobicity depending on the application to the other side of the woven or knitted fabric or the nonwoven fabric. However, it can be appropriately set according to the desired graft amount or graft ratio. For example, for acrylic acid, the graft amount is 0.012
About 0.029 mol / m ² (as a graft ratio based on the total weight of the woven or knitted fabric of 173 g / m ² 0.5 to 1.2% by weight)
The amount is about 100 to 200 times the desired graft amount in the dipping method.

In the case of the impregnation method, the loss of the monomer at the time of spraying is larger than that in the vapor phase method or the dipping method, so that the amount actually sprayed on the surface of the woven or knitted fabric or the nonwoven fabric is within the above range. The amount of spraying can be set appropriately.

Thus, a woven or knitted fabric or a non-woven fabric having only one surface modified, that is, a woven or knitted fabric or a nonwoven fabric having different front and back functions is obtained.

According to the method of the present invention in which plasma is generated in the absence of a woven or knitted fabric or a non-woven fabric and the plasma is applied to one side of the woven or knitted fabric or the nonwoven fabric, a treatment such as providing a protective layer on the other side is performed. It is possible to generate the active species only on one side without modifying the above, and it is possible to modify only one side. Further, according to the method of the present invention, even a thin woven or knitted fabric or a nonwoven fabric can be modified on only one side.
Therefore, the woven or knitted fabric or nonwoven fabric obtained by the method of the present invention has excellent front and back different functions. Further, the woven or knitted fabric or the nonwoven fabric obtained by the method of the present invention is excellent in the durability of the different functions on the front and back sides (specifically, the wash resistance), and particularly when the graft polymerization is performed by the impregnation method, the wash resistance is particularly high. It has excellent properties.

The woven or knitted or non-woven fabric of the present invention When the hydrophobic woven or knitted or non-woven fabric is graft-polymerized with a monomer having a hydrophilic group by the method of the present invention, a woven or knitted or non-woven fabric having excellent front and back different functions can be obtained. Depending on the type of woven or knitted fabric or nonwoven fabric, the type of monomer, etc., for example, a woven or knitted fabric or nonwoven fabric having the following physical properties (1) and (2) can be obtained. (1) Water absorption by JISL 1096A method is 3 seconds or less on one side (plasma irradiation surface) and 100 seconds or more on the other surface (plasma non-irradiation surface). (2) The number of hydrophilic groups on one side is 3 times the number of hydrophilic groups on the other side.
More than double.

The value of the above (2) can be calculated as follows, for example, by surface elemental analysis by ESCA.

That is, when a monomer having a carboxyl group is used as a grafting monomer, trifluoroethanol is reacted at about 60 to 70 ° C. for about 1 to 10 hours, and the carboxyl existing on the surface of the woven or knitted fabric or the nonwoven fabric is reacted. The group (hydrophilic group) is esterified, and the number (%) of fluorine atoms on the front (plasma-treated surface) and back (plasma-untreated surface) surfaces is measured. Since the number of fluorine atoms is proportional to the number of carboxyl groups (hydrophilic groups), the number of carboxyl groups on the front surface and the back surface can be calculated as a relative value by the number of fluorine atoms. When calculated in this way,
In the woven or knitted fabric or the nonwoven fabric of the present invention, the amount of hydrophilic groups on the surface is larger than the amount of hydrophilic groups on the back surface, and is usually about 3 times or more.

When a monomer having a hydrophilic group other than a carboxyl group is used as a grafting monomer, chemical modification is performed according to the kind of the hydrophilic group, and the relative hydrophilicity is determined by elemental analysis by ESCA. The amount of group can be calculated. The chemical modification can be carried out, for example, by using trifluoroacetic anhydride when the grafting monomer has a hydroxyl group or imino group, and by using pentafluorobenzaldehyde when it has an amino group.

When a monomer having an acidic group is graft-polymerized on a hydrophobic woven or knitted fabric or a nonwoven fabric and dyed with a cationic dye, one side (plasma-treated side) is dyed by a salt-forming bond with the acidic group. Since the other side is hardly dyed, a difference in color density occurs. Since the woven or knitted fabric or nonwoven fabric obtained by the method of the present invention has an acidic group on only one side, the difference in color density becomes larger than that of a woven or knitted fabric or nonwoven fabric modified on one side by a conventional method.

For example, a cationic dye [Estrol Red, trade name, manufactured by Sumitomo Chemical Co., Ltd.] is used for dyeing, and Sycomac (“SICOMUC”, registered trademark, Sumika Chemical Analysis Service, Ltd.)
When using a Macbeth spectrophotometer with 20 software, the color density of the front surface (plasma-irradiated surface = dyed surface) is 2 when the back surface (plasma-irradiated surface = undyed surface) is 100%.
It becomes about 100 to 500%.

[0069]

EXAMPLES The present invention will be described in more detail with reference to the following examples and test examples.

Example 1 (1) Plasma Treatment A woven fabric (hereinafter sometimes referred to as “fabric”) was subjected to plasma treatment using a continuous atmospheric pressure plasma treatment apparatus.

A polyester (PET) fabric [width 50 cm, length about 1 m,
A fabric weight of 173 g / m ² ] was attached. Mixed gas of helium and argon (helium: 9 SLM [Standard Litter p
er Minute], Argon 1 SLM) was introduced into the discharge space, and glow discharge plasma was generated at a high frequency (RF) power [750 W (frequency 13.56 MHz)] under atmospheric pressure. Irradiation was performed so that the plasma was blown out toward one side of the fabric, and the plasma treatment was continuously performed. An enlarged view of the irradiation part of the continuous plasma processing apparatus is shown in FIG. The irradiation area (B × W) was 12.5 mm × 500 mm, the distance between the cloth and the counter electrode (ground electrode) (A) was 6 mm, and the cloth feeding speed was 2 mm / min. The plasma treatment was continuously performed for about 8 hours.

(2) Grafting Treatment After completion of the plasma treatment, the cloth was removed from the roller, once taken out in the air (air), set in a graft polymerization apparatus, and subjected to a polymerization reaction treatment.

The plasma-treated cloth was set in a graft polymerization apparatus [vacuum exhaust apparatus capable of heating the entire chamber], and vacuum exhaust and N ₂ purge were repeated to sufficiently deaerate the air in the cloth to 0.1 Torr. Exhaust was stopped when the pressure became less than (about 13.3 Pa). Next, the acrylic acid in the glass container was heated to about 70 ° C., and N ₂ gas was bubbled through the mass flow, and acrylic acid monomer vapor was introduced into the apparatus together with N ₂ gas. When a predetermined amount of acrylic acid (100 ml) was introduced, the pressure inside the device became 30 to 40 Torr (about 4 to 5.3 kPa).
After the acrylic acid was introduced, the polymerization device (chamber) was heated so that the temperature of the cloth in the device was about 80 ° C. 24
After a period of time, the cloth was taken out from the device.

The amount of graft polymer of the obtained cloth was 0.5% by weight based on the total weight of the cloth.

Comparative Example 1 (1) Plasma Treatment As a comparative example, plasma treatment was performed using a parallel plate type atmospheric pressure plasma treatment apparatus (manufactured by Hirano Mitsuon Co., Ltd.) (a conceptual diagram thereof is shown in FIG. 5). Cloth between electrode plates (PE
T woven fabric, 10 × 10 cm ² ) is inserted and the inside of the plasma processing apparatus is filled with a predetermined plasma processing gas [helium gas 90 vo
1% argon gas 10 vol%], degassed, depressurized to 1 Torr (about 133 Pa), and maintained at atmospheric pressure with plasma gas. Plasma irradiation under atmospheric pressure in a plasma gas atmosphere [frequency 20 KHz, high frequency power 100 W,
Plasma irradiation time was 60 seconds].

(2) Grafting Treatment Next, the cloth was taken out from the apparatus and a graft polymerization reaction was performed. The polymerization reaction was carried out by gas phase graft polymerization using a polymerization tube having a capacity of 160 ml in which 3 to 4 Teflon pipes cut into 2 to 3 cm were placed at the bottom. 2 ml of acrylic acid as a hydrophilic monomer was placed in the polymerization tube. Next, the parallel plate atmospheric pressure plasma-treated cloth was inserted into a polymerization tube and placed on a Teflon pipe. The inside of the polymerization tube was replaced with nitrogen gas and degassed to 0.1 Torr (about 13.3 Pa)
The pressure was reduced to, and the pressure was maintained during the reaction. The reaction temperature is 7
It was carried out at 0 ° C. for 8 hours.

The amount of graft polymer of the obtained cloth was 0.5% by weight based on the total weight of the cloth.

Test Example 1 Water Absorption Test The water absorbency of the cloths obtained in Example 1 and Comparative Example 1 was evaluated by the JIS L 1096A method. The results are shown in Table 1.

[0079]

[Table 1]

^{* The} water absorption time was 1 second or less, and there was a dropping site that exceeded 1 second but was 3 seconds or less, but there was no site that exceeded 3 seconds.

From the results shown in Table 1, it can be seen that the fabric of Example 1 has excellent water-absorbing property on one side and almost no water-absorbing property on the other side. On the other hand, since the fabric of Comparative Example 1 is grafted on both sides and has hydrophilic groups, it is understood that both sides are water-absorbing and that different functions on the front and back sides are not obtained.

Test Example 2 Surface analysis by XPS After the carboxyl groups of acrylic acid present on the fabric surface obtained in Example 1 were esterified with trifluoroethanol, the surfaces of the plasma irradiation surface and the plasma non-irradiation surface were measured by XPS . Elemental analysis was performed. Also, for comparison,
Elemental analysis was also performed on the surface of the cloth before the plasma treatment that had been esterified.

The carboxyl group of acrylic acid is converted to --CH ₂ C.
In order to substitute with F ₃ and esterify, trifluoroethanol sealing treatment (65 ° C., 8 hours) was performed under the following conditions.

Sealed vial (20 cc) Trifluoroethanol 40 mg (0.02 mol / L) DCC 4 mg (0.001 mol / L) Pyridine 62 mg (0.04 mol / L) XPS was measured using Φ Quantum 2000. Was performed under the conditions of.

Analysis area: 100 μmΦ X intensity: 15 kV, 24.3 W Pass energy: 187.85 eV (wide) /23.50
(Narrow) The results are shown in Table 2.

[0086]

[Table 2]

Since the acrylic acid group was replaced by -CH ² CF ³ , the surface (plasma-treated surface) of the fabric of Example 1 had 3.6 times as many fluorine atoms as the back surface (plasma-untreated surface). It is present, and therefore, the hydrophilic group on the front surface can be calculated as 3.6 times that of the hydrophilic group on the back surface.

FIG. 6 shows the analysis result of the table of the fabric of Example 1.
The analysis result of the back side of the cloth of Example 1 is shown in FIG. 7, and the analysis result of the cloth before treatment is shown in FIG.

Test Example 3 Color Density The cloth treated in Example 1 and Comparative Example 1 was treated with a cationic dye [Estrol Red, trade name, Sumitomo Chemical Co., Ltd.].
Manufactured by the company] at about 95 ° C.

The fabric of Example 1 was dyed only on one side and not on the other side. On the other hand, the fabric of Comparative Example 1 was dyed on both sides, and no difference was visually observed in the degree of dyeing on each side.

After dyeing, the color densities of the front surface and the back surface of the fabric of Example 1 were measured by using the SICOMUC (registered trademark)
Sumika Chemical Analysis Center) 20 software built-in Macbeth spectrophotometer was used for measurement. When the color density of the back surface (plasma-irradiated surface = non-dyed surface) was set to 100%, the color density of the front surface (plasma-irradiated surface = dyed surface) was 318.1%.

Example 2 (1) Plasma treatment Polyester (PET) knitted fabric [width 50 cm, length about 1
m, basis weight 135 g / m ² ], feed speed 2.5 m
Plasma treatment was performed in the same manner as in (1) Plasma treatment of Example 1 except that m / min was set.

(2) Grafting Treatment Next, the cloth was taken out from the apparatus, placed in a polymerization reaction apparatus, and reduced in pressure to about 0.1 Torr (about 13.3 Pa), and then a graft polymerization reaction by an impregnation method was performed. Ikeuchi Co., Ltd. spray gun (fine fog generating nozzle BIM type) 1m
The cloth having a width of 0.5 m was moved at a speed of / min, and acrylic acid was sprayed on the plasma-treated surface of the cloth. Acrylic acid was sprayed together with nitrogen gas so that the spray rate was 0.5 L / min. After spraying, it was heated at a pressure of about 300 Torr (about 40 kPa) at 80 ° C. for 24 hours.

The amount of the graft polymer of the obtained cloth was 0.5% by weight based on the total weight of the cloth.

Test Example 4 Water Absorption and Washing Resistance Test Using the fabric treated in Example 2, the water absorption and washing resistance were evaluated. Washing is repeated 50 times according to JIS L-0217 Washing 103 method, and after 10 times and 50 times, the water absorption time of the front surface (plasma irradiation surface) and back surface (plasma non-irradiation surface) of JIS L-0217 -1096 Water absorption rate Measured according to the A method (dripping method). The results are shown in Table 3 below.

[0096]

[Table 3]

From the results shown in Table 3, it can be seen that the fabric of Example 2 has water absorbing property on one side and almost no water absorbing property on the other side, and has excellent front and back different functions. Further, it can be seen that the water absorbency of the surface is 1 second or less after washing 10 times and 50 times, and the water absorbency of the surface is maintained even after washing 50 times. Washing resistance is an important property when the cloth is put into practical use as clothes, and it is generally evaluated that the cloth can withstand 50 or more times of washing as a criterion of practicality.

Test Example 5 Evaluation of Grafting Ratio The cloth obtained in Example 2 was used to measure the grafting ratio. The grafting rate is measured using methylene blue (hereinafter referred to as “Mb”) [Mb method, GFDanidson and TPN
evell, The Journal of the Textile Institute, Trans
actions, p.T59, March 1948]. That is, when the fabric of Example 2 is immersed in the Mb solution, Mb ions react with the carboxyl groups on the fabric surface, and the concentration of the Mb solution decreases. Therefore, the concentration of the Mb solution was determined by measuring the absorbance, and the weight of the monomer reacted with the Mb ion was calculated.

The graft ratio can be generally obtained according to the following formula (1).

[0100]

[Equation 1]

Since the weight of the monomer reacted with Mb ion corresponds to "weight of cloth after treatment-weight of untreated cloth", the graft ratio was calculated by applying it to the above formula (1).

Grafting ratio was measured immediately after grafting and JI
S L-0217 Washing Measured according to method 103 after washing 5, 10, 30 and 50 times. The results are shown in Fig. 9.

From the results shown in FIG. 9, even after washing 50 times,
It can be seen that the grafted state is maintained.

[Brief description of drawings]

FIG. 1 is a model diagram of a water absorption / diffusion mechanism of cloth (woven or knitted fabric).

FIG. 2 is a conceptual diagram of a continuous atmospheric pressure plasma processing apparatus.

FIG. 3 is a conceptual diagram of a balloon type atmospheric pressure plasma processing apparatus.

FIG. 4 is a conceptual diagram of a plasma irradiation unit of the continuous atmospheric pressure plasma processing apparatus used in Example 1.

FIG. 5 is a conceptual diagram of a conventional parallel plate type plasma processing apparatus.

FIG. 6 is a diagram showing the results of surface analysis measurement in Test Example 2 (Example 1-Table).

FIG. 7 is a view showing the results of surface analysis measurement of Test Example 2 (Example 1-back).

FIG. 8 is a diagram showing a result of surface analysis measurement of Test Example 2 (untreated product).

FIG. 9 is a diagram showing the results of Test Example 5;

[Explanation of symbols]

(A) Model diagram of water absorption and diffusion of hydrophobic woven and knitted fabric (B) Model diagram of absorption and diffusion of woven and knitted fabric with hydrophilic both sides (C) Water absorption and diffusion of woven and knitted fabric having both hydrophilic and hydrophobic sides Model diagram (1) Hydrophobic region (2) Hydrophilic region (3) Water droplet (4) Moisture permeation layer 1: Discharge generation electrode 2: Matching device 3: Radio frequency power supply (RF) 4: Cooling system 5: Counter electrode 6 : Nozzle gas outlet 7: Plasma 8 and 9: Inorganic insulator 10: Plasma generation gas supply system 11: Diluting gas supply system 12: Discharge space 13: Object to be treated (woven or knitted fabric) 14: Exhaust system 15: Vacuum container (bell jar) 16 and 17: Insulator 18: Discharge generation electrode 19: Counter electrode 20: High frequency power supply 21: Matching device 22: Object to be processed (woven or knitted fabric)

─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Seiichi Kataoka 1-831 Midorigaoka, Ikeda City, Osaka Prefecture Institute of Industrial Science Osaka Institute of Industrial Technology (72) Inventor Noboru Saeki, Minamikagaya, Suminoe-ku, Osaka City, Osaka Prefecture 8-13 No. 13 Pearl Industry Co., Ltd. (72) Inventor Taku Fukada 3-8-13 Minamikagaya, Suminoe-ku, Osaka-shi, Osaka Prefecture Pearl Industry Co. Ltd. (72) Inventor Takuji Tatsumi Shimanouchi, Chuo-ku, Osaka-shi, Osaka Prefecture 1-11-32 Nisshin Textile Co., Ltd. (72) Inventor Nori Goto 1-13-132 Shimanouchi, Chuo-ku, Osaka-shi, Osaka Prefecture Nisshin Textile Co., Ltd. (56) Reference JP-A-11-256476 ( JP, A) JP 59-1406569 (JP, A) JP 1-21-2573 (JP, A) JP 8-109228 (JP, A) JP 9-296368 (JP, A) (58 ) Fields investigated (Int.Cl. ⁷ , DB name) D06M 10/00-15/715

Claims (3)

(57) [Claims] 1. A plasma generated between the atmospheric pressure plasma generating electrodes is applied to one side of a woven or knitted fabric or a non-woven fabric arranged outside the discharge space to generate an active species, and then the active species is a polymerizable monomer. A method for modifying one side of a woven or knitted fabric or a non-woven fabric by graft-polymerizing. 2. The method according to claim 1, wherein the polymerizable monomer is sprayed onto one side of the woven or knitted fabric or the nonwoven fabric when the polymerizable monomer is graft-polymerized to the active species. 3. A blow-out type atmospheric pressure plasma generator
Plasma generated between electrodes
Is irradiated on one side of a woven or knitted fabric or a nonwoven fabric.
The method according to claim 1, wherein