JPH0215662B2 - - Google Patents

Description

[Detailed Description of the Invention] Technical Field The present invention relates to fibrils, yarns, yarns, etc. whose fiber surfaces have been modified.
It relates to textiles such as cloth and final textile products.

Prior Art Conventionally, various studies have been conducted to improve the dyeability, texture, wettability, etc. of fibers.

For example, it is effective to create irregularities on the fiber surface to improve dyeability and texture, so the surface is chemically treated with acid or alkali and etched.
There were fibers whose surfaces were finely cut or raised. However, all types of fibers require many troublesome surface treatment steps, are difficult to control to obtain appropriate treatment results, and have the disadvantage that the strength of the fibers is extremely reduced, making it difficult to obtain fully satisfactory results. Not obtained.

In addition, some fibers were surface-treated by acid or alkali treatment (a type of wet treatment) to improve wettability. However, wet processing requires many processing steps and requires a lot of energy to dry the washed fibers. In addition, a large amount of treatment liquid is required, and the waste liquid must be treated to prevent the waste liquid from causing pollution problems. Furthermore, since it is a chemical treatment, the reaction tends to proceed inside the fibers, and there is a risk that the fiber strength will decrease.

Purpose The present invention was made to solve the problems with conventional textiles as described above, and its purpose is to improve color depth, wettability, washability, hygroscopicity, water absorption, washability, A new type of fiber with improved dyeability, texture, and other properties, without degrading the original properties and strength of the fiber, and with which surface treatment can be performed easily and at low cost with fewer steps. Our goal is to provide the following.

Structure: The fiber material of the present invention is obtained by etching the surface of the fiber by a sputter etching method in a gas atmosphere of 1×10 ^-4 to 8×10 ^-2 Torr, and then treating it with low-temperature plasma gas. That is.

EXAMPLE Hereinafter, an example in which the present invention is embodied in a cloth will be described with reference to FIG. 1. Reference numeral 1 denotes an etching device, and in this example, a high frequency sputtering device is used. Reference numeral 2 denotes a flat electrode, to which a high frequency voltage is applied from a high frequency power source 3.

Reference numeral 4 denotes a vacuum pump connected to the etching apparatus 1 via a valve 4a, and is used to reduce the pressure inside the apparatus 1 before sputter etching.
5 is an argon gas cylinder connected to the etching apparatus 1 via a valve 5a. Reference numeral 6 indicates a leak valve of the etching apparatus 1.

A cloth 7 is set so as to be in contact with the electrode 2 at the stretched portion, and is a polyester woven cloth dyed black and wound into a roll. Before this cloth 7 is set in the etching device 1,
Static electricity is removed as appropriate depending on the degree of charging.

Reference numeral 8 denotes a feeding mechanism for winding and feeding the roll-shaped cloth 7, which includes a feeding shaft 9 and a winding shaft 10, which are rotatably provided and on which the cloth 7 is set on the outer periphery, and the winding shaft 10. It is composed of a motor 11 for rotation and a deceleration transmission section 12 made of gears. The sputtering time per fixed area of the cloth 7 can be arbitrarily changed by adjusting the feed speed of the feed mechanism 8. Reference numeral 13 is a shield plate of the cloth 7, and the cloth 7 is designed so that only the stretched portion of the cloth 7 that is almost in contact with the electrode 2 is sputter etched.
The rolled portion of the cloth 7 is shielded.

In order to sputter-etch the surface of the cloth 7 using the etching apparatus 1 described above, first, the inside of the etching apparatus 1 is heated to 5×10 ^-4 Torr using the vacuum pump 4.
After reducing the pressure to a certain degree of vacuum, argon gas is introduced into the device 1 from the cylinder 5, and the inside of the device 1 is
×10 ^-3 Torr argon gas atmosphere was created. next,
When a high-frequency voltage was applied to electrode 2 and a high-frequency power of 100 W was applied, a discharge occurred, and argon molecules were excited and ionized, forming a plasma state. The excited argon ions collided with the surface of the fibers of the cloth 7, etching minute irregularities in each fiber constituting the cloth 7.

The mechanism of this etching is that argon ions collide with high energy against the carbon molecules of the polyester polymer that makes up the fibers, breaking molecular bonds and ejecting the carbon molecules as molecular order or macroscopic aggregates. it is conceivable that.

The cloth 7 is gradually fed by the feeding mechanism 8 during the etching process and is continuously processed, but in this embodiment, the etching time per fixed area of the cloth 7 is
The speed of the feed mechanism 8 was adjusted so that the time was 20 seconds.

By the way, in normal sputtering, metal molecules on the surface of an electrode (target) are ejected by high-energy ions, and the metal molecules are attached to an adherend (conventionally, a synthetic resin product, etc.). On the other hand, in this embodiment, molecules on the surface of the cloth 7 are scraped off using a sputtering device. Therefore, in the present invention, an etching method that satisfies the following requirements as in this embodiment is referred to as sputter etching.

Must be in a low-pressure specified gas atmosphere.

When a predetermined voltage is applied to the electrodes, a discharge occurs, and the gas is excited and ionized.

The gas ions collide with the object to be treated (in the present invention, a fibrous material) other than the electrode, and knock out the constituent molecules of the object.

As will be described later, the conditions for the sputter etching are not limited to those of this embodiment.

As described above, the cloth 7 that has been etched by the sputter etching method is subjected to a plasma gas treatment after the static electricity is appropriately removed. Next, the plasma gas processing will be explained with reference to FIG. 2. Reference numeral 21 is a cylinder filled with a processing gas, and in this embodiment, oxygen gas is used as the processing gas. 22 is a plasma generator connected to the cylinder 21 via a gas flow meter 23, and a high frequency power source 24 is connected thereto. High frequency power supply 2
4 generates microwaves of 2450 MHz, and the microwaves are output into the plasma generator 22. Inside the plasma generator 22, the processing gas is excited by the microwaves and dissociated into a plasma gas state, and the low temperature plasma gas is continuously flowed out.

Reference numeral 25 denotes a processing tank provided on the outflow side of the plasma generator 22, in which the etched cloth 7 is set in the form of a roll. 26 is a processing tank 25
It is a plasma gas injection member provided inside and connected to the plasma generator 22, and is configured to eject low-temperature plasma gas from a plurality of injection holes 27 arranged in parallel.

Reference numeral 28 denotes a feeding mechanism for winding and feeding the roll-shaped cloth 7, which, like the feeding mechanism 8 in the etching device 1, has a feeding shaft 29 and a winding shaft 3.
0, a motor 31, and a deceleration transmission section 32. Each of the injection holes 27 opens near the surface of the stretched portion of the cloth 7 fed by the feeding mechanism 28,
Plasma gas is sprayed over the entire width of the cloth 7. 33 is a shield plate for the cloth 7, which shields the rolled portion of the cloth 7 so that only the stretched portion of the cloth 7 is subjected to the plasma gas treatment.

34 is a leak valve provided in the processing tank 25. A vacuum pump 35 is connected to the processing tank 25 via a valve 36, and is used to reduce the pressure inside the processing tank 25 before plasma gas processing.

In order to treat the surface of the cloth 7 with plasma gas, first, the inside of the treatment tank 25 containing air is pumped with a vacuum pump.
Reduce the pressure to about 0.1Torr. Next, oxygen gas as a processing gas is supplied from the cylinder 21 to the plasma generator 22.
At the same time, the high frequency power is turned on and the frequency is
Microwaves of 2450 MHz and output of 600 W are applied to the plasma generator 22. The oxygen gas is easily excited into a plasma state by the microwave, becomes oxygen plasma gas, and is sent into the processing tank 25 at a low temperature and at a flow rate of 10/min.

The oxygen plasma gas is supplied to the injection hole 2 of the injection member 26.
7 and is sprayed onto the cloth 7. When the polyester fibers constituting the cloth 7 come into contact with oxygen plasma, functional groups such as carbonyl groups and carboxyl groups are generated on the surface due to the high activity of the oxygen plasma. Since minute irregularities are thus formed, the substantial surface area of the same surface increases, and the number of the functional groups increases by the increased surface area. Therefore, much more of the above-mentioned functional groups are produced than in the case where plasma gas treatment is performed without sputter etching. After being injected, the oxygen plasma gas flows through the processing tank 25 and then passes through the leak valve 34.
is continuously discharged (the flow rate is 10/min, the same as the inflow rate). Therefore, in this example, the atmospheric pressure inside the processing tank 25 was maintained at 0.3 Torr.

The cloth 7 is moved by the feeding mechanism 28 during the plasma gas treatment.
In this embodiment, the speed of the feeding mechanism 28 is adjusted so that the time required for treatment with oxygen plasma gas is 100 seconds per certain area of the cloth 7. adjusted.

Regarding the changes in the properties of the cloth 7 that has been subjected to the sputter etching and plasma gas treatment as described above, in comparison with the untreated cloth, firstly, the b value, which indicates the hue, has decreased by about 10%, and the color has changed. became darker. When converted into the amount of dye used, this corresponds to increasing the concentration of dye during dyeing by about 15%, indicating that the amount of dye used can be reduced. Visually, the hue has changed to a deep black. This is thought to be because light is scattered by the minute irregularities formed on the fiber surface by sputter etching, and a portion of the light is trapped in the minute concave portions, reducing the amount of light reflected. Conventional fibers etched with caustic soda, for example, have rough irregularities, so there is no light trapping effect and the hue remains almost the same.

Next, a wettability test was conducted by dropping 50 μm of water, and the water instantly permeated the treated cloth and spread into a circle with a diameter of about 1 cm. On the other hand, water beads appear on untreated cloth, and when the water evaporates to the extent that the water beads disappear, a circular stain (water) with a diameter of about 2 mm appears.
was seen. Therefore, wettability and water absorption,
It can be seen that the stainability was improved. This is because the hydrophilicity of the fiber surface increases due to the action of functional groups such as carbonyl groups and carboxyl groups introduced by plasma gas treatment, and the surface area of the fiber is substantially reduced by the minute irregularities introduced by sputter etching. This is a synergistic effect due to increased water absorption.

Similarly, the drying properties of the fibers are maintained while the hygroscopicity is improved. These effects are particularly remarkable in suede fibers such as the polyester fibers of this example.

Furthermore, when dyeing is performed after the sputter etching and plasma gas treatment, the dyeing property is greatly improved, and the hue, fading resistance, etc. are improved. This is because the adhesion of the dye to the fiber increases due to the substantial increase in the fiber surface area, the physical effect of micro-irregularities, the affinity of the functional groups, etc., and the amount of adhesion increases.It is also the synergistic effect of the above two treatments. It can be said.

Furthermore, the texture of the fibers is improved by the effects of minute irregularities and functional groups, resulting in a soft and supple feel. This effect is remarkable in artificial fibers with microscopically smooth surfaces as in this example, resulting in a texture similar to that of natural fibers such as cotton and wool.

In addition, due to the action of the functional groups, the treated cloth had an effect of preventing oil stains, and even when it was stained with oil, the washability was greatly improved.

Furthermore, since both processes are dry processes, the processing work can be performed easily and at low cost, and the processing conditions (type of sputter etching gas or plasma processing gas, pressure, applied voltage, processing time, etc.) can be controlled. Since these are also easy to adjust, arbitrary processing results can be obtained by adjusting these. Furthermore, since no treatment liquid is required, no pollution is caused.

In addition, in the plasma gas treatment, oxygen plasma gas is generated by the plasma generator 22 outside the treatment tank 25, and only low-temperature plasma gas is introduced into the treatment tank 25, so that the cloth 7 is not affected by the heat of the plasma gas. There is no performance deterioration.

Furthermore, since the plasma generator 22 uses microwaves, the processing gas can be excited extremely easily and efficiently, and the plasma gas will not be overheated.

It should be noted that the present invention is not limited to the configuration of the above-mentioned embodiment, and can be embodied as follows, for example.

(1) In addition to cloth, fibers in various stages such as raw fibers, threads, and final fiber products can be used. Furthermore, cloth is not limited to simply woven, knitted, or non-woven fabrics.
This also includes fabrics that have been given a luxurious feel by brushing or flocking, or have been made flame retardant by attaching phosphorus compounds.

(2) The fibers of the present invention include all kinds of fibers such as various natural fibers and synthetic fibers such as polyester, polyacrylic, polyamide, rayon, and cotton, other special fibers such as glass fibers and carbon fibers, and combinations thereof. .

(3) The sputter etching conditions of the present invention are as follows. In addition to argon gas, various gases that do not react with the fibers, such as inert gas such as neon and xenon, or nitrogen gas, may be used as the gas for forming the sputter etching atmosphere. The pressure of the gas can be selected between 1×10 ⁻⁴ and 8×10 ⁻² Torr. This is because if the gas pressure is outside this range, it will be difficult for discharge to occur, a plasma state will not be formed, and sputter etching will not be possible. The applied power is not particularly limited as long as sputter etching is possible, but it is usually 50W or more.
It is 10KW.

Furthermore, a DC sputtering apparatus may be used as the etching apparatus 1 instead of the high frequency sputtering apparatus, and sputter etching may be performed by applying a DC voltage.

(4) As a gas for plasma gas treatment, various gases such as nitrogen, ammonia, sulfur dioxide, methane, carbon tetrafluoride, ethane, propane, chlorine, bromine, helium, argon, and others can be used in addition to the above oxygen gas. .

For example, when carbon tetrafluoride gas is used, the surface of the fiber is treated with fluorine in addition to the above-mentioned functional groups, resulting in extremely high water repellency and improved durability.

Further, when ammonia gas or nitrogen gas is used, amino groups are introduced into the fiber surface in addition to the above-mentioned functional groups, so the wettability to water is greatly increased and the dyeability is also significantly improved.

In addition, by using gases such as sulfur dioxide, methane, ethane, propane, chlorine, and bromine, properties such as disaster prevention, airtightness, and slipperiness are improved.

(5) The plasma gas generation conditions are not particularly limited as long as they use microwaves that can easily and efficiently generate plasma, and the microwave frequency, output, processing gas flow rate, etc. can be changed arbitrarily. It is possible.

In addition, the flow rate of plasma gas, the pressure inside the processing tank,
The plasma treatment time and the like can also be changed arbitrarily.

Effects As detailed above, the present invention etches the fiber surface portion by the sputter etching method, and then
Low-temperature plasma gas treatment improves color depth, wettability, washability, hygroscopicity, water absorption, washability,
Many properties such as dyeability and texture are improved, and the original properties and strength of the fibers are not deteriorated. In addition, surface treatment can be performed easily and at low cost with fewer steps. play.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing a sputter etching method in an embodiment embodying the present invention, FIG. 2 is a schematic diagram also showing a plasma gas processing method, and FIG.
This figure is a perspective view of the main part in FIG. 2. Etching device...1, cloth...7, plasma generator...22, high frequency power source...24, processing tank...25.

Claims (1)

[Claims] 1. The surface area of the fiber is 1×10 ^-4 Torr to 8×10 ^-2 Torr.
A fibrous material characterized in that it is etched by a sputter etching method in a gas atmosphere and then treated with a low-temperature plasma gas. 2. The fibrous material according to claim 1, wherein the low-temperature plasma gas is excited and generated by microwaves.