CN106536816A - Method for producing surface-modified fiber material and surface-modified fiber material - Google Patents

Abstract

The present invention provides a method for producing a high-value, surface-modified fiber material by modifying the surface of natural and synthetic fibers derived from plants and animals, thereby leveraging the inherent properties of the fiber material and imparting new functionality. The method comprises depositing an inorganic material on the surface of the fiber material using a sol-gel reaction while moving the fiber material via an airflow. Preferably, the surface of the fiber material is irradiated with atmospheric pressure low-temperature plasma while the fiber material, with the inorganic material attached to its surface, is moved via an airflow.

Description

Method for producing surface-modified fiber material and surface-modified fiber material

technical field

The present invention relates to a method for producing a surface-modified fiber material (hereinafter also simply referred to as "manufacturing method") and a surface-modified fiber material. A method for producing a surface-modified fiber material in which fibers are highly functionalized to obtain a high-function fiber material, and the surface-modified fiber material obtained thereby.

Background technique

In recent years, in the field of fiber materials and products, in addition to the development of new chemical fiber materials, new functional and high-functional fiber materials (so-called high technology fiber) development. Various technologies have been proposed for imparting functionality obtained through product improvement until now to the fiber material itself as its raw material, for example, water-absorbent fiber with improved water absorption of the fiber material itself, and antibacterial fiber with added antibacterial properties , superfiber with strength capable of lifting a car of about 700kg, etc.

On the other hand, with the recent upsurge in respect for nature, the demand for natural fibers derived from animals and plants, such as silk and wool, has also been increasing for fiber materials. Also to such natural fibers, as long as the above-mentioned various functions can be imparted, it is possible to realize excellent fiber materials that have not been found in the past by making use of the characteristics of natural fibers that synthetic fibers do not have.

However, the above-mentioned conventional high-performance and high-functionalization technologies for fiber materials involve improvements in the structure of synthetic fibers themselves, and cannot be applied to natural fibers. Therefore, surface modification technology of fiber materials has been proposed as a high-functionalization technology of fiber materials that can be applied to synthetic fibers as well as natural fibers.

For example, Patent Document 1 discloses a titanium oxide-containing natural fiber whose fiber surface is plated with titanium oxide, and a method for producing the same.

prior art literature

patent documents

Patent Document 1: Japanese Reexamination No. 98/053132

Contents of the invention

The problem to be solved by the invention

However, the technology described in Patent Document 1 is also insufficient, and the realization of a higher-functional surface-modified fiber material has been sought.

Therefore, the object of the present invention is to provide a high-value-added fiber material that utilizes the original characteristics of the fiber material and imparts new functionality by modifying the surface of natural fiber materials derived from animals and plants and synthetic fibers. A method for producing a functional surface-modified fiber material and a surface-modified fiber material.

solutions to problems

As a result of intensive studies, the inventors of the present invention have found that the above-mentioned problems can be solved by adopting the following configuration, and have completed the present invention.

That is, the method for producing a surface-modified fiber material of the present invention is characterized in that the inorganic material is attached to the surface of the fiber material by a sol-gel reaction while the fiber material is moved by air flow.

In the production method of the present invention, it is preferable to irradiate the surface of the fiber material with atmospheric-pressure low-temperature plasma while moving the fiber material with the inorganic material adhered to the surface by air flow. In addition, in the production method of the present invention, titania, alumina, and ceramics can be suitably mentioned as the inorganic material. Furthermore, in the production method of the present invention, as the fiber material, natural fibers or synthetic fibers can be used, and among them, feathers, powder or microfibers made from cocoons, silk threads, wool, cotton, hemp, etc. can be suitably used. , pulp or synthetic fibers, particularly preferably feathers.

In addition, the surface-modified fiber material of the present invention is characterized in that it is produced by the above-mentioned production method of the present invention.

The effect of the invention

According to the present invention, not only synthetic fibers but also natural fibers can be utilized to impart new functionality to the original properties of fiber materials, and high-functional surface-modified fiber materials with high added value can be obtained.

Description of drawings

Fig. 1 is a schematic diagram of a treatment apparatus used for the adhesion treatment of titanium dioxide on the surface of a fiber material.

Fig. 2 is a schematic diagram of a treatment apparatus used for plasma irradiation treatment of a titanium dioxide-attached fiber material.

Fig. 3 is a schematic diagram of a treatment device used in an example for the adhesion treatment of titanium dioxide to the surface of down.

(a) and (b) of FIG. 4 are photographs showing Ti gels.

(a) and (b) of FIG. 5 are photographs showing untreated down, and (c) and (d) of FIG. 5 are photographs showing down with titanium dioxide attached.

(a) of FIG. 6 is a photogram of SEM of untreated down, and (b) of FIG. 6 is a photogram of SEM of down treated with titanium dioxide.

7( a ) is a spectrum showing the analysis results of EDX measurement of untreated down, and FIG. 7( b ) is a spectrum showing the analysis results of EDX measurement of titanium dioxide-treated down.

Fig. 8 is a schematic diagram of a treatment apparatus used in Examples for plasma irradiation treatment of titanium dioxide-attached down.

Fig. 9 is a schematic diagram showing the structure of four rows of plasma torches.

Fig. 10 is a partial sectional view showing the structure of the plasma torch.

(a) and (b) of FIG. 11 are explanatory diagrams of the heat retention test of down.

(a) of FIG. 12 is a graph which shows the temperature in the heat retention test of down, and FIG. 12 (b) is a graph which shows the temperature change in the heat retention test of down.

(a) of FIG. 13 is an explanatory diagram showing the state of the temperature change of each part of the quilt 55 minutes after the start of heating in Example 1, and (b) of FIG. 13 shows the state of the quilt 55 minutes after the start of heating of the comparative example An explanatory diagram of the state of temperature change in each part.

(a) of FIG. 14 is a graph which shows the change of the internal temperature of futon with respect to temperature, and (b) of FIG. 14 is a graph which shows the change of the internal temperature of futon with respect to temperature change.

Fig. 15 is a schematic diagram showing a processing device for processing down and down by blowing after washing.

Fig. 16 is an explanatory diagram showing the analysis results of the surface composition of each down obtained by XPS.

Figure 17 is the C1s narrow spectrum of titanium dioxide treated down before and after plasma treatment.

Figure 18 is the Ti2p narrow spectrum of titanium dioxide treated down before and after plasma treatment.

Fig. 19 is an explanatory diagram showing the analysis results of the surface composition of down and down treated with titanium dioxide adhesion and plasma irradiation for each number of washings obtained by XPS.

Fig. 20 is a graph showing changes in Ti concentration depending on the number of times of washing.

Fig. 21 is an explanatory diagram showing the analysis results of the surface composition of chemical fibers obtained by XPS.

Fig. 22 is an explanatory diagram showing the analysis results of the surface composition of the silk obtained by XPS.

Fig. 23 is an explanatory diagram showing the analysis results of the surface composition of wool obtained by XPS.

(a) and (b) of FIG. 24 are explanatory views which show the testing apparatus used for the rigidity test of down.

Fig. 25 is an explanatory diagram showing changes in rigidity before and after treatment for untreated down and down treated with titanium dioxide adhesion and plasma irradiation.

Fig. 26 is an explanatory diagram showing changes in rigidity before and after washing for untreated down and down treated with titanium dioxide adhesion and plasma irradiation.

Fig. 27 is an explanatory diagram showing changes in rigidity before and after blowing treatment for untreated down and down treated with titanium dioxide adhesion and plasma irradiation.

(a) and (b) of FIG. 28 are photographs showing down with alumina attached.

Fig. 29 is an explanatory view showing the analysis results of the surface composition of down and down before and after alumina treatment by XPS.

Figure 30 is the XPS spectra of down and down before and after alumina treatment.

detailed description

Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the drawings.

This embodiment is a case where the inorganic material attached to the surface of the fiber material by a sol-gel reaction is titanium dioxide. Hereinafter, the case where titanium dioxide is attached to the surface of the fiber material by the sol-gel reaction of the titanium compound while the fiber material is moved by air flow will be specifically described below.

In this embodiment, titanium dioxide is attached to the surface of the fibrous material while the fibrous material is moved by the air flow, so the entire fibrous material can be treated uniformly, and the fibrous material, especially natural fibers, can be maintained. The original shape and characteristics of the material are modified and the surface is modified, so high-quality surface-modified fiber materials can be obtained. Therefore, by using the surface-modified fiber material obtained by this embodiment as a raw material, it is possible to realize a high value-added surface-modified fiber product utilizing its functionality.

Here, specifically, the adhesion treatment of titanium dioxide (TiO ₂ , molecular weight 79.87) to the surface of the fiber material in this embodiment can use, for example, titanium tetraisopropoxide (TTIP, molecular weight 284.22) as a titanium compound and follow the following sol -Gel reaction to proceed.

Ti{OCH(CH ₃ ) ₂ } ₄ +2H ₂ O(water vapor)→TiO ₂ +4(CH ₃ ) ₂ CHOH

FIG. 1 shows a schematic diagram of a treatment apparatus used for the adhesion treatment of titanium dioxide to the surface of the fiber material in the method for producing a surface-modified fiber material according to this embodiment. The processing device shown in the figure has: a device main body 11, which is used for processing; a feeding port 12, which is used to send fiber materials into the device main body 11; a delivery port 13, which is used to send processed fiber materials from the device sending out from the main body 11; and an introduction port 14 for introducing titanium compound into the main body 11 of the device.

In the processing device shown in the figure, feeding and sending out of the fiber material to and from the device main body 11 are performed by airflow. Specifically, by flowing air at a speed of, for example, 500 cm/s to 5000 cm/s, particularly about 2000 cm/s, the fiber material can be moved along with the air. In addition, for example, an opening may be provided in the upper part of the apparatus main body 11, etc., and the fiber material may be directly put in and taken out from the opening, and there is no particular limitation.

After the fiber material is fed into the processing device 11 , a titanium compound is introduced into the processing device 11 from the introduction port 14 . At this time, the titanium compound can be introduced in a mist form by spraying into the apparatus main body 11 from the introduction port 14 as a solution of alcohol or the like. At this time, by spraying the solution of the titanium compound at high pressure, a conveying airflow rotating along the height direction can be generated in the device main body 11, and the fiber material filled in the device main body 11 can be moved by the conveying airflow, while the above-mentioned sol can be used. - Titanium dioxide produced by the gel reaction is attached to the surface of the fibrous material.

In this embodiment, it is preferable to further irradiate the surface of the fiber material having titanium dioxide attached to the surface with atmospheric-pressure low-temperature plasma. Thereby, the titanium dioxide adhered to the surface of the fiber material can be more firmly fixed on the surface of the fiber material, and the detachment of the titanium dioxide during the treatment after the surface modification can be more reliably suppressed, and the functionality imparted to the synthetic fiber and the natural fiber can be maintained for a long time.

Here, the atmospheric-pressure low-temperature plasma refers to plasma generated under atmospheric pressure and at a normal temperature of approximately 40° C. or lower. In the present invention, atmospheric pressure low-temperature plasma is used in the processing of fiber materials, so that decompression is not required, therefore, equipment costs and processing costs can be suppressed, and processing can be performed at normal temperature, so no damage to the object to be processed will be caused. The shape and characteristics of the fiber material cause damage. Such atmospheric-pressure low-temperature plasma irradiation treatment can be performed using, for example, an atmospheric-pressure room-temperature plasma jet generator CAPPLAT manufactured by Cressel Corporation. The plasma generation gas is not particularly limited, and various commonly used gases can be used, but argon gas is preferable from the viewpoint of cost.

FIG. 2 shows a schematic diagram of a treatment apparatus used for plasma irradiation treatment of a titanium dioxide-attached fiber material in the method for producing a surface-modified fiber material according to this embodiment. The processing device shown in the figure has: device main body 21, and it is used for processing; Sending port 22, it is used to send in the fiber material that adheres to titanium dioxide in device main body 21; The fiber material of titanium dioxide is sent out from the device main body 21; the irradiation device 24 is used to irradiate the fiber material in the device main body 21 with plasma;

In the processing apparatus shown in the figure, the fiber material to which titanium dioxide is attached is carried in and sent out from the apparatus main body 21 by airflow. Specifically, the air can be made to flow at a speed of, for example, 500 cm/s to 5000 cm/s, particularly about 2000 cm/s, and the fiber material can be moved along with the air.

Also in the device shown in FIG. 2 , as in the device shown in FIG. 1 , by introducing air from the gas inflow port 25 , it is possible to generate a conveying air flow that rotates in the height direction in the device main body 21 . Therefore, also in this embodiment, the plasma irradiation treatment can be performed while moving the titanium dioxide-attached fiber material by the conveying air flow, thereby enabling uniform treatment of the entire titanium dioxide-attached fiber material.

In addition, in this embodiment, it is possible to carry out the treatment while alternately switching the feeding and feeding of the fibrous material to and from the inside and outside of the device main body, and the introduction of the titanium compound or air in each device. That is, in each device, at first, in the state with the inlet port 14 or the gas inlet port 25 and the outlet port 13, 23 closed, the fiber material is sent into the device main body 11, 21 from the inlet port 12, 22 by air. enter. Thereafter, the supply ports 12 and 22 are closed, and a titanium compound or air is introduced from the introduction port 14 or the gas inflow port 25 to perform titanium dioxide deposition or plasma irradiation treatment. After the treatment is completed, the introduction port 14 or the gas inflow port 25 is closed, and the treated fibrous material is taken out from the delivery ports 13 and 23, whereby the fibrous material can be processed in batches. Here, in this embodiment, the positions of the inlet 12, the outlet 13, and the inlet 14 relative to the device main body 11, and the locations of the inlet 22, the outlet 23, the irradiation device 24, and the gas inlet 25 relative to the device The installation location of the main body 21 is not limited to the illustrated example, and it goes without saying that it can be appropriately changed as desired.

In addition, it is preferable to keep the inside of the nozzle or the like clean by washing the inside of the nozzle or the like with alcohol or the like after the titanium dioxide attachment treatment.

As the fiber material used in this embodiment, any fiber material including natural fibers and synthetic fibers can also be used, especially synthetic fibers that can achieve high functionality with almost no use of functional materials in the past, especially natural fibers That is, it is meaningful that the natural fiber material derived from animals and plants is the surface-modified fiber material of the base material. Examples of such fiber materials derived from animals and plants include feathers, powder or microfibers made from cocoons, silk threads, wool, cotton, hemp, and pulp. Here, the powder made of cocoon is not the raw silk drawn from the cocoon, but the cocoon itself is directly pulverized, which can be said to be a powder of silk, and the fine fiber made of cocoon is the fine fiber attached to the cocoon. Fine cocoon coat (fluff) on the surface of the cocoon. In addition, the silk thread includes both a single thread drawn from a cocoon and a thread obtained by spinning, and also includes a thread obtained by a special method, for example, SILK WEB (trade name (registered trademark), Mapepe Unit (Manufactured by Mappe Unit) Co., Ltd.) and the like. In addition, fiber materials obtained from fiber raw materials commonly used in paper products are also included in the present invention.

In the surface-modified fiber material obtained by this embodiment, the effect that the fiber material itself becomes bulky due to the adhesion of titanium dioxide is obtained. Among them, the bulkiness of feathers (Japanese: 宋高さ, フィルパワー) is used to indicate the quality. Therefore, by applying the present invention to feathers, there are advantages in that the bulkiness can be greatly improved, and low-quality and cheap feathers can be replaced. Obtaining high-quality feathers can contribute to the provision of high-quality and inexpensive feather products.

In the production method of this embodiment, the titanium dioxide attachment treatment is operated for 1 month and 20 days (160h), and 2t of down is processed using TTIP, so that the load capacity relative to the down can be 0.1% by mass to 1% by mass. It is implemented at a cost of 70,000 yen/month to 700,000 yen/month. In addition, the combined cost for the case of using the atmospheric pressure low-temperature plasma at the same time is about 60,000 yen/month, which has an advantage that the manufacturing cost is low.

As another embodiment of the present invention, the case where the inorganic material adhered to the surface of the fiber material by a sol-gel reaction is alumina.

In the case of this other embodiment, it can be the same as the above embodiment except that an aluminum compound, preferably aluminum isopropoxide, is used instead of the titanium compound in the above embodiment.

Also in the surface-modified fiber material obtained by this other embodiment, the fiber material itself becomes bulky due to the adhesion of alumina. Among them, by applying this to feathers, there are advantages in that bulkiness can be greatly improved, high-quality feathers can be obtained from low-quality and cheap feathers, and it can contribute to the provision of high-quality and inexpensive feather products.

Another embodiment of the present invention includes a case where the inorganic material adhered to the surface of the fiber material by a sol-gel reaction is ceramic.

In the case of this still another embodiment, except that a ceramic compound is used instead of the titanium compound in the above-mentioned embodiment, in the same manner as in the above-mentioned embodiment, in the obtained surface-modified fiber material, the fibers due to the adhesion of ceramics are also obtained. The effect in which the material itself becomes fluffy. Therefore, by applying it to feathers in the same way as titanium dioxide and alumina, the bulkiness can be greatly improved, and high-quality feathers can be obtained from low-quality and inexpensive feathers.

Example

Hereinafter, the present invention will be described in more detail using examples.

Example 1

(Production of Ti sol)

100 ml of titanium tetraisopropoxide (TTIP) was dissolved in 900 ml of methanol dehydrated with molecular sieves, and 10 ml of 1.5 M HCl aqueous solution was added and stirred to prepare a Ti sol.

For methanol and Ti sol, the N ₂ pressure was set at about 0.07 MPa, the weight was measured three times before and after spraying for 1 minute, and the average value was calculated, and the liquid spraying speed of the nozzle was confirmed. As a result, the liquid spray rate was 11.4 g/min for methanol, whereas Ti sol had a high viscosity, so the liquid spray rate was slightly reduced to 8.5 g/min, and there was no significant change. As shown in the following Table 1, the time required for the titanium dioxide attachment treatment to down as a fiber material was calculated from the above-mentioned liquid spray speed and Ti sol concentration. As a result, the time required to add 1% by mass of _TiO to 5 g of down The time of 11 seconds was about 11 seconds, therefore, in the following Example 1, the processing time was set to 15 seconds.

[Table 1]

(Titanium dioxide adhesion treatment device)

Using the processing apparatus of the structure shown in FIG. 3, the titanium dioxide attachment process was performed to the down which is a fiber material. The processing device shown in the figure has: device main body 31, it is used to carry out the attachment of titanium dioxide to eider down; The port 34 is used to introduce TTIP into the main body 31 of the device.

The inlet 32 for air injection is connected to a blower 36 via a valve 35 . In addition, a nozzle 37 for injecting the titanium compound is disposed at the inlet 34, and the flow path 39a connected to the nozzle 37 can communicate with the flow path 39b on the atmosphere side or the flow path 39c on the titanium compound side by switching the three-way cock valve 38. . The flow path 39c can also communicate with the flow path 39d on the Ti sol side or the flow path 39e on the methanol side by switching the three-way stopcock 40, and the Ti sol container 41 and the methanol container 42 are connected to the _N2 balloon 43. Furthermore, the delivery port 33 is connected to a storage unit 44 for storing processed down. Furthermore, an opening 45 for feeding down is provided on the upper part of the device main body 31, and a mesh part M for gas discharge is provided on the upper part of the device main body 31 and the upper part of the storage part 44, respectively.

(Titanium dioxide adhesion treatment)

First, with the valve 35 of the delivery port 32 and the delivery port 33 closed, 5 g of down is injected into the inside of the device main body 31 from the opening 45 of the device main body 31 . Next, the opening 45 is closed, the three-way stopcock 38 is switched so that the flow path 39 a on the nozzle 37 side communicates with the flow path 39 b on the atmosphere side, and N ₂ gas flows to the nozzle 37 . The N ₂ gas pressure during the treatment was set at about 0.07 MPa.

Next, after switching the three-way cock 40 so that the flow path 39c on the three-way cock 38 side communicates with the flow path 39d on the Ti sol side, the three-way cock 38 is switched to the flow path 39a and the flow path 39c of the nozzle 37. Connected, the mist of Ti sol was sprayed into the apparatus main body 31 for 15 seconds. Thereby, while rotating and moving the down in the apparatus main body 31 in the height direction, an attachment process of attaching titanium dioxide to the surface of the down was performed.

After the processing was completed, the three-way cock 40 was switched so that the flow path 39c on the three-way cock 38 side communicated with the flow path 39e on the methanol side, and the nozzle 37 was cleaned with methanol. Thereafter, the three-way stopcock 38 is switched so that the flow path 39 a of the nozzle 37 communicates with the flow path 39 b on the air side, and the methanol accumulated in the nozzle 37 is discharged. Then stop the N gas, close the opening 45 and the screen ₂₄ provided on the top of the device main body 31, and operate the blower 36 with the valve 35 opened to transfer the processed down to the storage unit 44.

(a) of Fig. 4, (b) show the photogram of the digital microscope (VHX-600 manufactured by Keyence Co., Ltd.) of Ti gel, and (a) of Fig. 5, (b) show the picture of untreated down. Photographs of a digital microscope (VHX-600 manufactured by KEYENCE Corporation), and (c) and (d) of FIG. 5 show photographs of a digital microscope (VHX-600 manufactured by KEYENCE Corporation) of down with titanium dioxide . As shown in the figure, it can be seen that the feather structure of the titanium dioxide-attached down after treatment does not change even when the untreated down and the titanium dioxide-attached down are compared, and the feather structure is maintained. In addition, observation with a digital microscope revealed that the Ti gel was in the form of a film. In the down treated with titanium dioxide, no powdery deposits were observed, so it is considered that titanium dioxide coats the surface of the down in a thin film. 6( a ) shows a photograph of an SEM (scanning electron microscope) of untreated down, and FIG. 6( b ) shows a photograph of a SEM (scanning electron microscope) of titania-treated down. According to the photograph, it was observed that the surface of the untreated down was smooth and nothing was attached, while the surface of the titanium dioxide-treated down was smooth but had cracks and a small amount of particle-like deposits. Moreover, (a) of FIG. 7 shows a spectrum showing the analysis results of the EDX (energy dispersive X-ray spectrometry) measurement of untreated down and down, and (b) of FIG. 7 shows the EDX ( Spectrum of analysis results measured by energy dispersive X-ray spectrometry). From this result, it was found that titanium was not detected in the EDX measurement even in the untreated down, but titanium was detected in the deposit part in the down with titanium dioxide attached thereto. From these results, it is considered that there is almost no difference in the shape of the titanium dioxide-treated down from the untreated state, and it was confirmed that titanium dioxide forms a uniform coating to cover the down.

(Plasma irradiation treatment device)

The plasma irradiation process was performed on the down with titanium dioxide adhered using the processing apparatus of the structure shown in FIG. The processing device shown in the figure possesses: a device main body 51, which is used to carry out plasma irradiation treatment to eider down; an injection port 52 for air injection; a delivery port 53, which is used to send out processed eider down from the device main body 51; a device 54 for irradiating down with plasma in the device main body 51 ; and a gas inflow port 55 for allowing air to flow into the device main body 51 .

The inlet 52 for air injection is connected to a blower 56 . In addition, the delivery port 53 is connected to a storage unit 58 for storing processed down through a valve 57 . As the storage unit 58, a cloth bag is used. Furthermore, an opening 59 for feeding down and a mesh part M for gas discharge are provided on the upper part of the device main body 51 . Furthermore, the irradiation device 54 is connected to a high-voltage power supply HV. As the irradiation device 54 , an atmospheric-pressure room-temperature plasma jet generator CAPPLAT (manufactured by Kure-Siro Co., Ltd.) equipped with four rows of plasma torches as shown in FIG. 9 was used.

The four rows of plasma torches shown in FIG. 9 are formed by arranging four plasma torches 61 in parallel at intervals of 40 mm. In the figure, reference numeral 62 denotes an acrylic plate, reference numeral 63 denotes a connector, and reference numeral 64 denotes a vinyl chloride tube. In addition, FIG. 10 shows a partial cross-sectional view showing the structure of the plasma torch 61 . As shown in the figure, the plasma torch 61 is equipped with: a glass capillary tube 65; a Cu tube (8 mm in outer diameter, 7 mm in inner diameter, high voltage electrode) 66 covering the outer periphery; a double-layer silicone tube ( 12 mm outer diameter, 8 mm inner diameter and 16 mm outer diameter, 12 mm inner diameter) 67 ; and a silicone tube 68 covering the glass capillary 65 on the other end side of the Cu tube 66 . In addition, a spring clip 69 was attached to the silicone tube 68 , and a Cu tape (20 mm in width, ground electrode) 70 and a metal mesh (150 mesh) 71 were arranged on the side of the double-layered silicone tube 67 .

In addition, as the plasma irradiation conditions, a voltage of ±8 kV was applied in a pulse form at 20 kHz, and Ar gas at 20 LPM (l/min) was used as the plasma gas.

(plasma irradiation treatment)

First, with the valve 57 closed, 5 g of titanium dioxide-treated down was injected into the device body 51 from the opening 59 of the device body 51 . Next, the opening 59 is closed to allow air to flow in from the gas inlet 55 . When the down is not loosened, air is injected from the delivery port 52 using the blower 56 .

Next, under atmospheric pressure and room temperature conditions, Ar gas was supplied to the plasma torch of the irradiation device 54 and a high voltage was applied, and the down was irradiated for 30 seconds while the down was rotated and moved in the height direction in the device main body 51 by air. Clock plasma. Next, the supply of Ar gas and air is stopped, the mesh portion M is blocked, and the blower 56 is operated with the valve 57 opened to transfer the processed down to the storage portion 58 .

Furthermore, chemical fiber (polyester), thread, and wool were treated in the same manner as described above.

(Insulation test of down)

Duvet samples with a size of 500 mm×380 mm in Example 1 and Comparative Example were produced using 20 g of down treated with titanium dioxide adhesion treatment and plasma irradiation treatment and 20 g of untreated down. The following evaluations were performed using this quilt sample.

First, the electric heating belt ( 40mm) to about 40°C. After measuring the temperature of each futon before heating, as shown in FIG. 11( a ), place a 40° C. 83 on. As shown in (b) of FIG. 11 , arrange paper guides 84 on top of the futon 81, and measure the temperature of the surface (outside) of the futon 81 with a radiation thermometer in the order of the numbers of the paper guides 84 after 55 minutes from the start of heating. determined. In addition, only the position 1 of the paper guide 84 was measured every 10 minutes after heating was started.

(a) of FIG. 12 shows a graph showing the measurement results of the temperature of the surface of the futon at position 1 of the paper guide with respect to temperature, and (b) of FIG. Graph showing the measurement results of the surface temperature of the futon at position 1. In addition, FIG. 13( a ) shows an explanatory diagram showing the state of temperature change of each part of the quilt 55 minutes after the start of heating in Example 1, and FIG. 13( b ) shows a representation showing a comparative example. An explanatory diagram of the state of temperature change of each part of the futon 55 minutes after the start of heating. 14( a ) shows a graph showing changes in the internal temperature of the futon with respect to temperature, and FIG. 14( b ) shows a graph showing changes in the internal temperature of the futon with respect to temperature changes.

As a result, in the comparative example using untreated down, the surface temperature increased by approximately 4°C over time, but in Example 1 using treated down, it did not rise by 2°C or more. From this, it can be seen that the thermal insulation of the processed down is higher than that of the untreated down, and it will not radiate heat to the outside of the quilt.

In addition, when the temperature of the electric heating belt 82 set to about 40° C. is put in the futon 81 , the temperature rises. For treated down, it is difficult to dissipate heat, and the temperature is higher compared to untreated down.

(Washing resistance test of treated down)

First, a cotton cloth having a size of 450 mm×100 mm was folded in half, both sides were sewn together, 3 g of down was put in it, and the remaining hem was sewn up to prepare a washing sample. i) Dissolve 5 ml of a neutral detergent in 2 L of water (about 25° C.), put in a sample for washing, squeeze and wash 40 times, and then dehydrate. ii) Next, the washing step of washing and dehydrating the washing sample by squeezing it in water 40 times was repeated twice. After repeating the above i) and ii) 10 times, it was dried overnight with a dryer at 60°C.

(Air treatment after washing of processed down)

The air-air treatment of washed down was performed using the air-air treatment apparatus shown in FIG. 15 . The illustrated device includes: a device body 91 for blowing down; a blower 92 for sending air into the device body 91 ; and a valve 93 . In addition, the upper part of the device body 91 is provided with: an opening 94 for feeding down into the device body 91 ; and a mesh part M for discharging air in the device body 91 .

First, the down is taken out from the above-mentioned washed cotton cloth, and the down is put into the device main body 91 from the opening 94 using a funnel, and then the opening 94 is closed. Then, close the valve 93, make the blower 92 work, and the eiderdown in the processing device 91 has been blown for 10 minutes (air velocity 1600cm/s). Afterwards, the down is taken out from the processing device 91 .

(XPS determination of down)

The surface composition of untreated down, down with titanium dioxide attached, and down treated with plasma after titanium dioxide was attached was analyzed by XPS (X-ray Photoelectron Spectroscopy). As an apparatus, ESCA5600 manufactured by Perkin Elmer was used, and the conditions of X-ray source Mg Kα14kV 400W and TOA45° were used. The analysis results of the surface composition of each down obtained by XPS are shown in FIG. 16 . In addition, Fig. 17 and Fig. 18 show the C1s and Ti2p narrow spectra of titanium dioxide-treated down before and after the plasma treatment.

From the results shown in FIG. 16 , it can be seen that the surface of the down is coated with titanium by performing the titanium dioxide treatment. In addition, it can be estimated from the results in Figures 17 and 18 that the feathers do not deteriorate by plasma treatment of titanium dioxide-treated down, but the peak position of Ti shifts to the high energy side and is close to 459eV of _TiO2 , and the amount of impurities decreases up.

In addition, FIG. 19 shows the analysis results of the surface composition for each number of washing times from 1 to 10 times for down and down treated with titanium dioxide adhesion and plasma irradiation by XPS, and FIG. A graph of the change in Ti concentration induced. Based on these results, it can be estimated that the Ti concentration in the titania-attached/plasma-irradiated down after washing does not change much compared to that of the titania-attached/plasma-irradiated down before washing, and that titanium does not come off by washing.

On the other hand, the surface composition of chemical fibers, silk threads, and wool treated in the same way as down was analyzed by XPS. FIGS. 21 to 23 show the analysis results of the surface compositions of chemical fibers, silk threads, and wool obtained by XPS, respectively. From the results shown in FIGS. 21 to 23 , it can be seen that by performing the titanium dioxide treatment, the respective surfaces of the chemical fiber, the thread, and the wool are in a titanium-coated state.

(Rigidity test of down)

Changes in rigidity before and after treatment, changes in rigidity before and after washing, and changes in rigidity before and after blowing treatment were evaluated for untreated down and down treated with titanium dioxide adhesion and plasma irradiation. Specifically, i) As shown in (a) of FIG. 24 , put 1.5 g of down D into an acrylic tube 101 with an outer diameter of 49 mm, an inner diameter of 45 mm, and a height of 500 mm, and place a cap (2.5 g, made of foamed styrene) 102 and a weight (50 g) 103 were placed on the down D, and the height _h1 of the down D was measured. Then, ii) as shown in (b) of FIG. 24 , the weight 103 and the cover 102 _were removed, and the height h2 of the down D was measured again. After loosening the crushed down, the steps of i) and ii) were repeated about 10 times. The results are shown in FIGS. 25 to 27 .

From the results in the figure, it can be seen that the titanium dioxide-adhered and plasma-irradiated down was less deformed and had higher rigidity than the untreated down even when a weight was placed on it. Also, recovery after weight removal occurs immediately, but not a huge recovery. It can be seen that when the elastic modulus is calculated from the deformation, the weight of the weight, and the cross-sectional area, the elastic modulus of the titanium dioxide-adhered and plasma-irradiated down is higher than that of the untreated down, and it is high quality.

It can be seen that after washing, the down treated with titanium dioxide adhesion and plasma irradiation has higher rigidity than the untreated down. It can be seen that the elastic modulus of down treated with titanium dioxide adhesion and plasma irradiation is also high, and the treatment effect remains even after washing. In addition, after washing, the difference between the untreated down and the down treated with titanium dioxide adhesion and plasma irradiation becomes small, but the difference between the untreated down and the down treated with titanium dioxide adhesion and plasma irradiation is reduced by blowing the washed down. The difference becomes larger again.

Example 2

Al sol was produced in the same manner as in Example 1 except that aluminum isopropoxide was used instead of titanium tetraisopropoxide. Next, in the same manner as in Example 1, an alumina adhesion treatment was performed.

In (a) and (b) of FIG. 28 , photographs of down with alumina adhered thereto are shown by a digital microscope (VHX-600 manufactured by KEYENCE Corporation). As shown in the illustration, even when comparing the untreated down of FIG. 28 and the down with alumina adhered, the feather structure does not change, and the feather structure is maintained.

In addition, the results of analyzing the surface composition of untreated down and alumina-attached down by XPS in the same manner as in Example 1 are shown in FIG. 29 . In addition, FIG. 30 shows XPS spectra before and after the alumina treatment.

From the results shown in FIG. 29 and FIG. 30 , it can be seen that the down surface is coated with alumina by performing the alumina treatment. From this, it can be seen that the same down as the titania treatment in Example 1 was obtained by the alumina treatment. Furthermore, the same content was confirmed also in ceramic processing.

Explanation of reference signs

11, 21, 31, 51, 91, the main body of the device; 12, 22, the inlet; 13, 23, 33, 53, the outlet; 14, 34, the inlet; 24, 54, the irradiation device; 25, 55, the gas Inflow port; 32, 52, injection port; 35, 57, 93, valve; 36, 56, 92, blower; 37, nozzle; 38, 40, three-way cock valve; 39a～39e, flow path; 41, Ti sol container; 42, methanol container; 43, _N2 air bag; 44, 58, receiving part; 45, 59, 94, opening; 61, plasma torch; 62, acrylic plate; 63, connector; 64, Vinyl chloride tube; 65, glass capillary tube; 66, Cu tube; 67, organic silicon tube; 68, organic silicon tube; 69, spring clip; 70, Cu belt; 71, metal screen; 81, bedding; ; 83, pad; 84, paper guide; 101, acrylic tube; 102, cover; 103, weight; M, screen section; D, feather.

Claims (13)

1. A method for manufacturing a surface-modified fiber material, characterized in that, While the fiber material is moved by air flow, the inorganic material is attached to the surface of the fiber material by sol-gel reaction. 2. the manufacture method of surface modified fiber material according to claim 1, wherein, Titanium dioxide is attached to the surface of the fiber material by utilizing the sol-gel reaction of the titanium compound while the fiber material is moved by the air flow. 3. the manufacture method of surface modified fiber material according to claim 2, wherein, The surface of the fiber material was irradiated with atmospheric-pressure low-temperature plasma while moving the fiber material with titanium dioxide adhered to the surface by air flow. 4. The manufacture method of the surface-modified fiber material according to claim 2 or 3, wherein, Titanium tetraisopropoxide was used as the titanium compound. 5. the manufacture method of surface modified fiber material according to claim 1, wherein, Alumina is attached to the surface of the fiber material by the sol-gel reaction of the aluminum compound while the fiber material is moved by the air flow. 6. the manufacture method of surface modified fiber material according to claim 5, wherein, The surface of the fiber material was irradiated with atmospheric-pressure low-temperature plasma while moving the fiber material with alumina adhered to the surface by air flow. 7. The manufacture method of the surface-modified fiber material according to claim 5 or 6, wherein, Aluminum isopropoxide was used as the aluminum compound. 8. The manufacture method of surface modified fiber material according to claim 1, wherein, While the fiber material is moved by air flow, ceramics are attached to the surface of the fiber material by utilizing the sol-gel reaction of the ceramic compound. 9. The manufacture method of surface modified fiber material according to claim 8, wherein, The surface of the fiber material is irradiated with atmospheric-pressure low-temperature plasma while moving the fiber material with the ceramic adhered to the surface by air flow. 10. The method for producing a surface-modified fiber material according to any one of claims 1 to 9, wherein, Natural fibers or synthetic fibers are used as the fiber material. 11. The manufacture method of surface modified fiber material according to claim 10, wherein, Feather, cocoon-based powder or fine fiber, silk thread, wool, cotton, hemp, pulp or synthetic fiber are used as the fiber material. 12. The manufacture method of surface modified fiber material according to claim 11, wherein, Feathers are used as the fiber material. 13. A surface modified fiber material, characterized in that, The surface-modified fiber material is produced by the production method described in any one of claims 1-12.