TWI719943B - Method for manufacturing surface-modified fiber material and surface-modified fiber material - Google Patents

Abstract

The present invention provides a surface modification of natural fiber materials and synthetic fibers that are derived from plants, while utilizing the original characteristics of fiber materials on the one hand, and imparting new functions and high-performance surface modification with high added value. Manufacturing method of fiber material and surface modification fiber material.

The present invention is a method for manufacturing surface-modified fibrous materials. The fibrous materials are moved by air flow, and inorganic materials are attached to the surface of fibrous materials through sol-gel reaction. Preferably, the surface of the fiber material is irradiated with atmospheric pressure low-temperature plasma while moving the fiber material on which the inorganic material is attached to the surface through the airflow.

Description

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

The present invention relates to a method for manufacturing surface-modified fiber materials (hereinafter also referred to as "manufacturing methods") and surface-modified fiber materials. In detail, it relates to surface modification of natural fiber materials and synthetic fiber materials derived from plants and animals. High-quality and high-functionality to obtain a high-performance fiber material surface-modified fiber material manufacturing method and the resulting surface-modified fiber material.

In recent years, in fiber materials. In the product field, in addition to the development of new chemical fiber materials, the development of high-functional fiber materials (so-called high-tech fibers) that improve the fiber material itself and impart new functionality (so-called high-tech fibers) is also popular. For example, water-absorbent fibers that improve the water absorption of the fiber material itself, or antibacterial fibers with added antibacterial properties, super fibers that have the strength to hang about 700 kg of automobiles, etc., which have been used as products so far, will be given the functional properties obtained through improvements. There have been many proposals for the technology of the raw material fiber material itself.

On the other hand, with the recent surge in naturalist orientation, the demand for fiber materials from natural fibers from plants such as silk or wool has also increased. About this kind of natural fiber, if it can also give such The above-mentioned various functions can utilize the characteristics of natural fibers that synthetic fibers do not have, and can realize excellent fiber materials that were not available in the past.

However, the above-mentioned high-performance and high-functionality technology of the conventional fiber materials is related to the improvement of the structure of the synthetic fiber itself, and cannot be applied to natural fibers. Therefore, as a high-performance technology for fiber materials that can be applied to synthetic fibers, and of course, can also be applied to natural fibers, surface modification technologies for fiber materials have been proposed.

For example, Patent Document 1 discloses a titanium oxide-containing natural fiber obtained by plating the surface of the fiber with titanium oxide and a manufacturing method thereof.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Re-list 98/053132 Gazette

However, the technology described in Patent Document 1 is not sufficient, and a surface-modified fiber material with higher performance is required.

Therefore, the object of the present invention is to provide a high-performance, high-performance, high-performance, high-value-added, new-functional and high-value-added product by modifying the surface of natural fiber materials and synthetic fibers that are derived from plants, while making use of the original characteristics of fiber materials. Manufacturing method of surface-modified fiber material and surface-modified fiber material.

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

That is, the method for manufacturing the surface-modified fiber material of the present invention is characterized by moving the fiber material through the airflow, and attaching the inorganic material to the surface of the fiber material by the sol-gel reaction.

In the manufacturing method of the present invention, it is preferable to further irradiate the surface of the fiber material with atmospheric pressure and low-temperature plasma while moving the aforementioned fiber material on which the inorganic material is adhered to the surface through the air flow. Furthermore, in the production method of the present invention, as the aforementioned inorganic material, titanium oxide, aluminum oxide, and ceramics can be preferably exemplified. Furthermore, in the manufacturing method of the present invention, natural fibers or synthetic fibers can be used as the aforementioned fiber material. Among them, powders or microfibers, spun silk, wool, cotton, and hemp made of feathers and cocoons as raw materials can be preferably used. , Pulp or synthetic fibers, especially feathers.

In addition, the characteristics of the surface-modified fiber material of the present invention are manufactured by the above-mentioned manufacturing method of the present invention.

According to the present invention, not only synthetic fibers, but also natural fibers can utilize the original characteristics of fiber materials and impart new functions, thereby obtaining high-performance surface-modified fiber materials with high added value.

11, 21, 31, 51, 91‧‧‧Device body

12, 22‧‧‧Entrance

13, 23, 33, 53‧‧‧Exit

14, 34‧‧‧Inlet

24, 54‧‧‧ Irradiation device

25, 55‧‧‧Gas inlet

32, 52‧‧‧Injection port

35, 57, 93‧‧‧valve

36、56、92‧‧‧Hair dryer

37‧‧‧Nozzle

38、40‧‧‧Three-way stopcock

39a~39e‧‧‧Flow Path

41‧‧‧Ti sol container

42‧‧‧Methanol Container

43‧‧‧N ₂ balloon

44, 58‧‧‧Containment Department

45, 59, 94‧‧‧ opening

61‧‧‧Plasma spray gun

62‧‧‧Acrylic board

63‧‧‧Connector

64‧‧‧Vinyl chloride pipe

65‧‧‧glass capillary

66‧‧‧Cu catheter

67‧‧‧Polysiloxane tube

68‧‧‧Polysiloxane tube

69‧‧‧Spring Clip

70‧‧‧Cu tape

71‧‧‧Metal Screen

81‧‧‧cloth group

82‧‧‧Band heater

83‧‧‧Gasket

84‧‧‧Paper guide sheet

101‧‧‧Acrylic catheter

102‧‧‧cover

103‧‧‧Weight

M‧‧‧Screen Department

D‧‧‧Goose down

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

Fig. 2 is a schematic diagram of a treatment device used for plasma irradiation treatment of a fibrous material attached with titanium oxide.

Fig. 3 is a schematic diagram of a treatment device used in the embodiment for the titanium oxide adhesion treatment on the surface of the goose down.

Figure 4 (a) and (b) are photographs showing Ti gel.

Figure 5 (a) and (b) are photographs showing untreated goose down, and (c) and (d) are photographs showing goose down with titanium oxide attached.

Figure 6 (a) is a SEM photograph of untreated goose down and (b) titanium oxide treated goose down.

Figure 7 (a) is a spectrum diagram of the analysis results of untreated goose down and (b) titanium oxide treated goose down by EDX measurement.

Fig. 8 is a schematic diagram of a treatment device used for plasma irradiation treatment of goose down to which titanium oxide adhered in the embodiment.

Figure 9 is a schematic diagram showing the configuration of 4 continuous plasma spray guns.

Figure 10 is a partial cross-sectional view showing the structure of the plasma spray gun.

Figure 11 (a), (b) are explanatory diagrams about the heat retention test of goose down.

Figure 12 is a graph showing (a) temperature and (b) temperature changes in the heat preservation test of goose down.

Fig. 13 is an explanatory diagram showing (a) the temperature change state of each part of the cloth dough 55 minutes after the start of heating for Example 1 and (b) the comparative example.

Figure 14 shows the inside of the cloth group for (a) temperature and (b) temperature changes Graph of temperature changes.

Fig. 15 is a schematic diagram showing the treatment device used for the air blowing treatment after washing the goose down.

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

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

Figure 18 is a narrow frequency graph of Ti2p before and after plasma treatment of goose down treated with titanium oxide.

Figure 19 shows the adhesion to titanium oxide obtained by XPS. An explanatory diagram of the analysis results of the surface composition of the goose down treated by plasma irradiation per washing times.

Figure 20 is a graph showing changes in Ti concentration due to the number of washes.

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

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

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

Figure 24 (a) and (b) are explanatory diagrams showing the display device used in the rigidity test of goose down.

Figure 25 shows the adhesion of untreated goose down and titanium oxide. An explanatory diagram of the rigidity changes before and after treatment of goose down treated by plasma irradiation.

Figure 26 shows the adhesion of untreated goose down and titanium oxide. Plasma photo An explanatory diagram of the rigidity changes of the shot-treated goose down before and after washing.

Figure 27 shows the adhesion of untreated goose down and titanium oxide. An explanatory diagram of the rigidity changes of goose down treated by plasma irradiation before and after the air blow.

Figure 28 (a) and (b) are photographs showing goose down attached to alumina.

Figure 29 is an explanatory diagram showing the analysis results of the surface composition of the goose down before and after alumina treatment obtained by XPS.

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

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

In this embodiment, the inorganic material attached to the surface of the fiber material by the sol-gel reaction is made of titanium oxide. Hereinafter, when the surface modification of the fiber material is performed, the case where the fiber material is moved through the air flow and the titanium oxide is attached to the surface of the fiber material by the sol-gel reaction of the titanium oxide compound is described in detail.

In this embodiment, since the fibrous material is moved by the airflow and titanium oxide is adhered to the surface, the entire fibrous material can be treated uniformly, and the original shape and characteristics of the fibrous material, especially the natural fiber material, can be maintained. After surface modification, high-quality surface-modified fiber materials can be obtained. Therefore, by using the surface-modified fiber material obtained in this embodiment as a raw material, its function can be utilized, and a surface-modified fiber product with high added value can be realized.

_{Here, the adhesion treatment of titanium oxide (TiO 2} , molecular weight 79.87) on the surface of the fiber material in this embodiment can be specifically, for example, titanium tetraisopropoxide (TTIP, molecular weight 284.22) as the titanium compound, according to the following The sol-gel reaction proceeds.

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

FIG. 1 is a schematic diagram showing a processing device used for the titanium oxide adhesion treatment on the surface of the fiber material in the method of manufacturing the surface-modified fiber material of this embodiment. The processing device shown in the figure has a device body 11 for processing, an inlet 12 for feeding fiber material into the device body 11, an outlet 13 for sending the processed fiber material out of the device body 11, and a device body 11 for processing. The introduction port 14 of the titanium compound is introduced into the main body 11 of the device.

In the processing device shown in the figure, the feeding of the fiber material into and out of the device body 11 is performed by air flow. Specifically, for example, the air may flow at a speed of 500 to 5000 cm/s, especially about 2000 cm/s, and the fiber material can be moved by riding on the air. In addition, the fiber material can be provided with an opening in the upper portion of the device body 11, for example, and the fiber material can 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, the titanium oxide compound is introduced into the processing device 11 from the inlet 14. At this time, the titanium compound is a solution of alcohol or the like, and can be introduced in the form of a mist by spraying into the device body 11 from the inlet 14. At this time, the solution of the titanium compound is sprayed at a high pressure to produce a conveyance that rotates in the height direction in the main body 11 of the device. The air flow causes the fibrous material filled in the device body 11 to move through the conveying air flow, while attaching the titanium oxide generated by the above-mentioned sol-gel reaction to the surface of the fibrous material.

In this embodiment, it is preferable to further perform atmospheric pressure low-temperature plasma irradiation on the surface of the fiber material with titanium oxide adhered to the surface. As a result, the titanium oxide attached to the surface of the fiber material can be more strongly fixed to the fiber surface material, and the peeling of the titanium oxide during the treatment after the surface modification can be suppressed more reliably, and the application of the titanium oxide to the synthetic fiber and natural The function of fiber.

Here, the so-called low-temperature plasma at atmospheric pressure refers to plasma generated at room temperature below 40°C under atmospheric pressure. In the present invention, by using atmospheric pressure low-temperature plasma in the processing of the fiber material, the equipment cost and the processing cost can be suppressed because there is no need to reduce the pressure, and since the processing can be performed at room temperature, it will not damage the processed object. The shape and characteristics of the fiber material. Such atmospheric pressure and low-temperature plasma irradiation treatment can be performed using, for example, an atmospheric pressure and normal-temperature plasma spray generator CAPPLAT manufactured by CRESUR (stock). The plasma-generated gas is not particularly limited, and various gases commonly used can be used, but from the viewpoint of cost, argon gas is preferred.

Fig. 2 is a schematic diagram showing a processing device used for plasma irradiation treatment of a fibrous material adhered with titanium oxide in the method of manufacturing a surface-modified fibrous material of the embodiment. The processing device shown in the figure is equipped with a device body 21 for processing, a feed port 22 for feeding titanium oxide-attached fibrous material into the device body 21, and a processed fibrous material attached to the titanium oxide from the device body 21.的送出出口23、For pairing An irradiation device 24 for plasma irradiation of the fiber material in the main body 21 and a gas inlet 25 for flowing air into the main body 21 of the device.

In the processing device shown in the figure, the feeding of the fibrous material attached with titanium oxide to the device body 21 and the feeding from the device body 21 are performed by air flow. Specifically, for example, air is flowed at a speed of 500 to 5000 cm/s, especially about 2000 cm/s, and the fiber material is moved by the air by riding on the air.

In the device shown in FIG. 2, similar to the device shown in FIG. 1, by introducing air from the gas inlet 25, a conveying airflow rotating in the height direction is generated in the device body 21. Therefore, in this embodiment, in the plasma irradiation treatment, the titanium oxide-attached fibrous material can also be carried out while moving through the conveying air flow, whereby the entire titanium oxide-attached fibrous material can be treated uniformly.

Furthermore, in this embodiment, the feeding and feeding of the fiber material into and out of the device body and the introduction of the titanium compound or gas in each device can be performed while alternately switching. That is, in each device, the fiber material is fed into the main body 11, 21 of the apparatus body 11, 21 through the air through the inlets 12, 22 in a state where the inlet 14 or the gas inlet 25, and the outlets 13, 23 are closed. Subsequently, the inlets 12 and 22 are closed, a titanium compound or air is introduced from the inlet 14 or the gas inlet 25, and titanium oxide adhesion or plasma irradiation treatment is performed. After the treatment is completed, the inlet 14 or the gas inlet 25 is closed, and the treated fiber material is taken out from the outlets 13, 23, and the fiber material can be processed in batch mode. Here, in this embodiment, the installation parts of the inlet 12, outlet 13 and inlet 14 of the device body 11 The positions and the installation locations of the inlet 22, outlet 23, irradiation device 24, and gas inlet 25 to the main body 21 of the device are not limited to the examples shown in the drawings, and it goes without saying that they can be changed as needed.

In addition, after the titanium oxide adhesion treatment, it is preferable to use alcohol or the like to clean the inside of the nozzle and the like to keep it clean.

As the fiber material used in this embodiment, any fiber material including natural fibers and synthetic fibers can also be used. However, in the past, high-function synthetic fibers using functional materials have hardly been used, especially natural fibers that are derived from Natural fiber materials of animals and plants are meaningful in terms of the possible use of surface-modified fiber materials for base materials. Examples of the fibrous material from the animal plant include feathers, powder or microfibers using silkworm cocoons as raw materials, spun silk, wool, cotton, hemp, and pulp. Here, the so-called powder made of silkworm cocoons as a raw material means that the cocoon itself is directly pulverized without drawing new silk from the cocoon, and it can be described as a powder of viscose. The so-called microfibers made of silkworm cocoons as a raw material means the fine feathers attached to the surface of the cocoon. . In addition, the so-called spun silk includes both a spun silk drawn from the cocoon and spun spun silk, and may also include spun silk obtained by a special method, such as SILK WEB (trade name (registered trademark), MAPEPE UNIT (shares) system) and so on. Furthermore, fiber materials obtained from fiber raw materials generally used in paper products are also included in the present invention.

In the surface-modified fiber material obtained by this embodiment, the effect of making the fiber material itself bulky is obtained by attaching titanium oxide. Among them, feathers are characterized by their fluffy properties (filling power). Therefore, the present invention is applied to feathers, which can greatly improve fluffy properties, and can be cheap from low quality. Feathers obtain high-quality feathers, which can help provide high-quality and cheap feather products.

In the manufacturing method of this embodiment, the titanium oxide adhesion treatment can be operated for 1 month and 20 days (160 hours), and 2t goose down treatment is performed using TTIP. The supporting amount of the goose down is 0.1-1% by mass, and the cost is 70,000 yen~ The cost of 700,000 yen/month is implemented. In addition, the cumulative cost of using atmospheric pressure low-temperature plasma is about 60,000 yen/month, which has the advantage of low manufacturing cost.

As for other embodiments of the present invention, the case where the inorganic material attached to the surface of the fiber material by sol-gel reaction is made of alumina can be exemplified.

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

The surface-modified fiber material obtained by this other embodiment also obtains the effect of making the fiber material itself fluffy by the adhesion of alumina. Among them, by applying it to feathers, the fluffiness can be greatly improved, and high-quality feathers can be obtained from low-quality cheap feathers, which can help provide the advantages of high-quality and cheap feather products.

As for the other embodiments of the present invention, a case where the inorganic material attached to the surface of the fiber material by sol-gel reaction is made of ceramic can be exemplified.

In this and other embodiments, in addition to using a ceramic compound instead of the titanium compound in the above embodiment, it can be similar to the above embodiment. At the same time, the obtained surface-modified fiber material also obtains the effect of making the fiber material itself fluffy through the adhesion of ceramics. Therefore, as with titanium oxide and aluminum oxide, by applying to feathers, the bulkiness can be greatly improved, and high-quality feathers can be obtained from low-quality cheap feathers.

[Example]

the following. Examples are used to illustrate the present invention in more detail.

[Example 1] (Production of Ti Sol)

Dissolve 100 ml of titanium tetraisopropoxide (TTIP) in 900 ml of methanol dehydrated by molecular sieve, add 10 ml of 1.5M HCl aqueous solution and stir to prepare Ti sol.

The weight of methanol and Ti sol was _{measured three times before and after spraying for 1 minute at a N 2} pressure of approximately 0.07 MPa, and the average value was calculated, and the liquid spray rate of the nozzle was confirmed. As a result, compared with the case where methanol is 11.4 g/min, Ti sol has a higher viscosity or 8.5 g/min, which slightly reduces the liquid spray rate, but there is no significant change. As shown in Table 1 below, the time required for titanium oxide adhesion treatment to goose 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 TiO ₂ to 5g of goose down was approximately It is 11 seconds, so in Example 1 below, the processing time is set to 15 seconds.

(Titanium Oxide Adhesion Treatment Device)

Using the processing device of the configuration shown in Fig. 3, the goose down as the fiber material was subjected to titanium oxide adhesion treatment. The processing device shown in the figure has a device body 31 for attaching titanium oxide to the goose down, an injection port 32 for air injection, a delivery port 33 for sending the processed goose down from the device body 31, and a device body 31 for use in the device body 31 Lead into the inlet 34 of TTIP.

In the inlet 32 for air injection, a blower 36 is connected through a valve 35. In addition, a nozzle 37 for spraying titanium compound is arranged at the inlet 34, and the flow path 39a connected to the nozzle 37 is switched by the three-way stopcock 38 to become the flow path 39b on the atmospheric side or the flow path 39c on the titanium compound side. Connected. The flow path 39c is further switched by the three-way stopcock 40 to be able to communicate with the flow path 39d on the Ti sol side or the flow path 39e on the methanol side, and the N ₂ balloon 43 is connected to the Ti sol container 41 and the methanol container 42. Furthermore, the delivery port 33 is connected to a receiving portion 44 for receiving the processed goose down. Furthermore, the upper part of the device body 31 is provided with an opening 45 for putting goose down, and the upper part of the device body 31 and the upper part of the accommodating part 44 are respectively provided with a screen part M for gas discharge.

(Titanium oxide adhesion treatment)

First, in a state where the valve 35 of the delivery port 32 and the delivery port 33 are closed, 5 g of goose down is inserted into the device body 31 from the opening 45 of the device body 31. Next, the opening 45 is plugged, the three-way stopcock 38 is switched so that the flow path 39a on the nozzle 37 side and the atmosphere side flow path 39b communicate, and N ₂ gas is introduced into the nozzle 37. _{The N 2} gas pressure during the treatment is set to about 0.07 MPa.

After the three-way stopcock 40 is switched so that the flow path 39c on the side of the three-way stopcock 38 communicates with the flow path 39d on the Ti sol side, the three-way stopcock 38 is switched so that the flow path 39a on the side of the nozzle 37 communicates with the flow path 39c, and The Ti sol aerosol is sprayed in the device body 31 for 15 seconds. Thereby, the goose down is rotated and moved in the height direction inside the device body 31, while the titanium oxide adhesion treatment is performed on the surface of the goose down.

After the treatment is completed, the three-way stopcock 40 is switched so that the flow path 39c on the side of the three-way stopcock 38 communicates with the flow path 39e on the methanol side, and the nozzle 37 is cleaned with methanol. Subsequently, the three-way stopcock 38 is switched so that the flow path 39a on the side of the nozzle 37 communicates with the air side flow path 39d, and the methanol accumulated in the nozzle 37 is discharged. Furthermore, the N ₂ gas is stopped, the opening 45 and the screen M provided in the upper part of the device main body 31 are closed, and the blower 36 is actuated with the valve 35 opened, and the treated goose down is transferred to the receiving part 44.

Figure 4(a) and (b) show Ti sol, Figure 5(a), (b) show untreated goose down, and Figure 5(c), (d) show the digits of goose down with titanium oxide attached Photograph of microscope (VHX-600 manufactured by KEYENCE Co., Ltd.). As shown in the figure, compare the untreated goose down with the goose down with titanium oxide attached. There is no change in the feather structure of the goose down with titanium oxide after treatment, and it can be seen that the feather structure is maintained. In addition, by observation with a digital microscope, it can be seen that the Ti sol is in the form of a thin film. In the goose down treated with titanium oxide, since no powdery deposits were confirmed, it is thought that the titanium oxide coats the surface of the goose down in a thin film. Furthermore, the SEM (scanning electron microscope) photographs of (a) untreated goose down and (b) titanium oxide treated goose down are shown in FIG. 6. It can be observed from the photograph that the surface of the untreated goose down is smooth without any adhesion. On the other hand, although the surface of the goose down treated with titanium oxide is smooth, it has cracks and slightly particulate deposits. Furthermore, FIG. 7 shows the spectrum of the analysis result of (a) untreated goose down and (b) titanium oxide treated goose down by EDX (Energy Dispersive X-ray Spectroscopy) measurement. From this result, it can be seen that titanium was not detected in the untreated goose down even if measured by EDX, and titanium was detected in the deposit portion of the goose down on which titanium oxide adhered. From these results, it is considered that there is almost no difference between the shape of the goose down treated with titanium oxide and the untreated state, and it is confirmed that the goose down is covered with titanium oxide as a homogeneous film.

(Plasma irradiation processing device)

Using the processing device of the configuration shown in Fig. 8, plasma irradiation treatment was performed on the goose down to which titanium oxide adhered. The processing device shown in the figure is equipped with a device body 51 for plasma irradiation treatment of goose down, an injection port 52 for air injection, a delivery port 53 for sending the processed goose down from the device body 51, and an injection port 53 for sending the processed goose down from the device body 51. An irradiation device 54 for plasma irradiation of the goose down, and a gas inlet 55 for flowing air into the body 51 of the device.

A blower 56 is connected to the inlet 52 for air injection. And the delivery port 53 is connected to the receiving part for accommodating the processed goose down through the valve 57 58. As the accommodating part 58, a cloth bag is used. Furthermore, an opening 59 for putting goose down and a screen M for discharging gas are provided on the upper part of the main body 51 of the device. Furthermore, the irradiation device 54 is connected to a high-voltage power supply HV. As the irradiation device 54, the atmospheric pressure and normal temperature plasma spray generator CAPPLAT (manufactured by CRESUR Co., Ltd.) equipped with 4 continuous plasma spray guns as shown in FIG. 9 was used.

The 4-continuous plasma spray gun shown in Fig. 9 is formed by arranging 4 plasma spray guns 61 side by side at 40mm intervals. The symbol 62 in the figure indicates an acrylic plate, 63 indicates a connector, and 64 indicates a vinyl chloride tube. 10 shows a partial cross-sectional view showing the structure of the plasma spray gun 61. As shown in the figure, the plasma spray gun 61 is equipped with a glass capillary 65, a Cu tube (outer diameter 8mm, inner diameter 7mm, high voltage electrode) 66 covering the outer circumference, and a two-layer silicone tube (outer diameter) covering one end of the Cu tube 66 12mm, inner diameter 8mm and outer diameter 16mm, inner diameter 12mm) 67, a polysilicon tube 68 covered with a glass capillary 65 at the other end of the Cu tube 66. A pinchcock 69 is installed on the silicone tube 68, and a Cu tape (width 20mm, ground electrode) 70 and a metal screen (150 mesh) 71 are arranged on the side of the two-layer silicone tube 67.

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

(Plasma irradiation treatment)

First, with the valve 57 closed, 5 g of goose down treated with titanium oxide is put into the device body 51 from the opening 59 of the device body 51. then, The opening 59 is plugged, and air flows in from the gas inlet 55. When the goose down is not untied, a hair dryer 56 is used to inject air from the inlet 52.

Next, under the conditions of atmospheric pressure and room temperature, Ar gas is supplied to the plasma spray gun of the irradiation device 54 and a high voltage is applied. The air is used in the device body 51 to rotate the goose down in the height direction, and the goose down is irradiated with the plasma 30. second. Next, the supply of Ar gas and air is stopped, the screen part M is plugged, and the blower 56 is actuated with the valve 57 opened to transfer the treated goose down to the receiving part 58.

Furthermore, the chemical fiber (polyester), spun silk, and wool were processed in the same manner according to the above method.

(Goose down heat preservation test)

Using 20 g of goose down treated with titanium oxide adhesion treatment and plasma irradiation treatment and untreated goose down, respectively, fabric mass samples with a size of 500 mm×380 mm in Example 1 and Comparative Example were produced. The following evaluation was performed using this cloth sample.

80mm，40mm)調節至約40℃。測定加熱前之各布團之溫度後，如圖11(a)所示，於布團81之下方，以位於布團81之中央部分之方式放置40℃之帶式加熱器82，並放置於墊片83上。如圖11(b)所示，於布團81上配置紙導引片84，開始加熱後55分鐘後，依紙導引片84之編號順序以放射溫度計測定布團81之弓起面(外側)之溫度。且，僅針對紙導引片84之位置1自加熱開始後每10分鐘進行溫 度測定。 First, the band heater (

80mm, 40mm) adjusted to about 40°C. After measuring the temperature of each cloth group before heating, as shown in Figure 11(a), under the cloth group 81, place a 40°C band heater 82 in the central part of the cloth group 81, and place it on On the gasket 83. As shown in Figure 11(b), the paper guide piece 84 is arranged on the cloth group 81. 55 minutes after heating starts, the bowed surface (outer side) of the cloth group 81 is measured by a radiation thermometer in the order of the paper guide piece 84 number. ) Of the temperature. In addition, only the position 1 of the paper guide piece 84 is subjected to temperature measurement every 10 minutes after the start of heating.

Fig. 12 shows a graph showing the temperature measurement results of the fabric bundle at position 1 of the paper guide sheet against (a) temperature and (b) temperature changes. In addition, FIG. 13 shows an explanatory diagram showing the temperature change state of each part of the cloth dough 55 minutes after the start of heating for (a) Example 1 and (b) Comparative Example. Furthermore, FIG. 14 shows a graph showing the change in the internal temperature of the cloth with respect to (a) temperature and (b) temperature change.

As a result, in the comparative example using untreated goose down, the surface temperature rose to close to 4°C over time, but Example 1 using treated goose down did not rise by more than 2°C. It can be seen from these that the heat preservation of the treated goose down is higher than that of the untreated goose down, and the heat does not escape to the outside of the cloth.

In addition, the temperature of the band heater 82 set to about 40°C increases when it enters the cloth group 81. In the processed goose down, the heat is not easy to escape, and the temperature becomes higher than that in the unprocessed goose down.

(Washing resistance test of treated goose down)

First, fold a cotton cloth with a size of 450mm×100mm in half and sew it on both sides, put 3g of goose down in it, and sew the remaining sides to make a washing sample. i) Dissolve 5ml of neutral lotion in 2L of water (about 25°C), put in the washing sample, squeeze and wash for 40 times, and then dehydrate. ii) Next, the washing sample was squeezed and washed in water 40 times, and the dehydration washing step was repeated twice. After repeating the above i) and ii) 10 times, it was dried in a dryer at 60°C overnight.

(Blowing treatment after washing goose down)

Use the blowing treatment device shown in Figure 15 to perform the blowing treatment of the washed goose down. The device shown in the figure includes a device body 91 for blowing goose down, a blower 92 for sending air into the device body 91, and a valve 93. And on the upper part of the device body 91, there are provided an opening 94 for putting goose down into the device body 91 and a screen portion M for discharging the air in the device body 91.

First, take out the goose down from the cotton cloth that has been washed, and use a funnel to put the goose down into the device body 91 from the opening 94 to close the opening 94. Next, the valve 93 is closed, the blower 92 is activated, and the goose down in the processing device 91 is blown for 10 minutes (air flow rate 1600 cm/s). Subsequently, the goose down is taken out from the processing device 91.

(XPS determination of goose down)

By XPS (X-ray photoelectron spectroscopy), the surface composition of untreated goose down, goose down with titanium oxide attached, and goose down with plasma treatment after attachment of titanium oxide were analyzed. As the device, ESCA5600 manufactured by Perkin Elmer was used, and the conditions were set as X-ray source Mg Kα 14kV 400W, TOA 45°. Figure 16 shows the analysis results of the surface composition of each goose down obtained by XPS. In addition, Fig. 17 and Fig. 18 show the C1s and Ti2p narrow-band diagrams of the goose down treated with titanium oxide before and after plasma treatment.

It can be seen from the results shown in FIG. 16 that the surface of the goose down is coated with titanium by the titanium oxide treatment. And, the results can be seen from FIG. 18 of FIG. 17, the processing of the titanium oxide by plasma processing of goose feathers deterioration does not occur, on the other hand, Ti of a high energy side of the peak position shifted close to the TiO ₂ 459eV, It is estimated that the amount of impurities has decreased.

In addition, Figure 19 shows the adhesion of titanium oxide obtained by XPS. The surface composition analysis results for each washing times of 1 to 10 times of plasma irradiation treatment of goose down are shown in Fig. 20 as a graph of Ti concentration changes caused by washing several times. From these results, it can be seen that compared to the attachment of titanium oxide before washing. Plasma irradiates the goose down, and the titanium oxide adheres after washing. The Ti concentration of the goose down treated by plasma irradiation did not change excessively, and it is presumed that the goose down will not fall off due to washing.

On the other hand, the surface composition of chemical fiber, spun silk and wool treated in the same way as goose down was analyzed by XPS. Figures 21-23 show the analysis results of the surface composition of chemical fiber, spun silk and wool obtained by XPS. From the results shown in Figures 21 to 23, it can be seen that by performing the titanium oxide treatment, the surfaces of the chemical fiber, spun silk, and wool are all in a state of being coated with titanium.

(Rigidity test of goose down)

For adhesion of untreated goose down and titanium oxide. Plasma irradiation treatment of goose down was evaluated separately before and after the treatment, the rigidity change before and after washing, and the rigidity change before and after the blowing treatment. Specifically, i) as shown in Figure 24(a), 1.5g of goose down D is put into the acrylic catheter 101 with an outer diameter of 49mm, an inner diameter of 45mm, and a height of 500mm, and a cover (2.5g, hair) is placed on the goose down D. _{Measure the height h 1 of} goose down D in the state of foamed polystyrene 102 and weight (50 g) 103. Subsequently, ii) as shown in Fig. 24(b), remove the weight 103 and the cover 102, and measure the height h _{2 of the} goose down D again. After unwrapping the crushed goose down, repeat steps i) and ii) about 10 times. The results are shown in Figure 25 to Figure 27.

From the results in the figure, compared with untreated goose down, titanium oxide adheres. The goose down treated by plasma irradiation did not break even if a weight was placed, and it was found that the rigidity was high. Moreover, it caused a response immediately after removing the weight, but there was not much response. When calculating the elastic modulus from the deformation, the weight of the weight, and the cross-sectional area, the titanium oxide adheres compared to the untreated goose down. The goose down treated by plasma irradiation is relatively high, and it can be seen that it becomes high quality.

It can be seen that even after washing, titanium oxide adheres. The rigidity of plasma-irradiated goose down is also higher than that of untreated goose down. The modulus of elasticity is also the adhesion of titanium oxide. The plasma irradiation treatment of goose down is relatively high, and it can be seen that the effect of the washing treatment still remains. Moreover, untreated goose down adheres to titanium oxide after washing. The difference between the goose down treated by plasma irradiation is reduced, but when the washed goose down is blown, the untreated goose down adheres to the titanium oxide. The difference in the plasma irradiation treatment of goose down becomes larger again.

Example 2

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

Figure 28 (a) and (b) respectively show the photographs of the digital microscope (VHX-600 manufactured by Keyence Co., Ltd.) of alumina-attached goose down. As shown in the figure, comparing the untreated goose down of Fig. 28 with the goose down with alumina adherence, there is no change in the feather structure, and it can be seen that the feather structure is maintained.

Also, the untreated goose was analyzed by XPS in the same way as in Example 1. The results of the surface composition of the goose down adhered to the down and alumina are shown in Figure 29. In addition, the XPS spectra before and after alumina treatment are shown in FIG. 30.

From the results shown in Figs. 29 and 30, it can be seen that the surface of the goose down can be coated with alumina by performing alumina treatment. From this, it can be seen that the same goose down as the titanium oxide treatment of Example 1 can also be obtained by alumina treatment. Furthermore, the same applies to the confirmation of ceramic processing.

Claims (13)

A method for manufacturing surface-modified fibrous materials, which is characterized by: while passing the air flow to move the fibrous material, while using the sol-gel reaction to make the inorganic material adhere to the surface of the fibrous material; While the fiber material moves, the surface of the fiber material is irradiated with atmospheric pressure low-temperature plasma. For example, the method for manufacturing a surface-modified fiber material of claim 1, wherein while the fiber material is moved by the air flow, titanium oxide is attached to the surface of the fiber material by the sol-gel reaction of the titanium compound. According to the method for manufacturing a surface-modified fiber material of claim 2, wherein the surface of the fiber material is irradiated with atmospheric pressure low-temperature plasma while moving the fiber material with titanium oxide attached to the surface through the airflow. The method for producing a surface-modified fiber material according to claim 2 or 3, wherein titanium tetraisopropoxide is used as the aforementioned titanium compound. For example, the method for manufacturing a surface-modified fibrous material of claim 1, wherein while the fibrous material is moved by air flow, alumina is attached to the surface of the fibrous material through the sol-gel reaction of the aluminum compound. For example, the method for manufacturing a surface-modified fiber material of claim 5, wherein the surface of the fiber material is irradiated with atmospheric pressure and low-temperature plasma while moving the fiber material with alumina adhered to the surface by air flow. The method for producing a surface-modified fiber material according to claim 5 or 6, wherein aluminum isopropoxide is used as the aforementioned aluminum compound. Such as the manufacturing method of surface-modified fiber material of claim 1, wherein while the fiber material is moved through the airflow, the ceramic compound is dissolved at the same time. The glue-gel reaction makes the ceramic adhere to the surface of the fiber material. The method for manufacturing a surface-modified fiber material according to claim 8, wherein the surface of the fiber material is irradiated with atmospheric pressure and low-temperature plasma while moving the fiber material on which the ceramic is attached to the surface by air flow. The method for manufacturing a surface-modified fiber material according to any one of claims 1 to 3, wherein natural fiber or synthetic fiber is used as the aforementioned fiber material. For example, the method for manufacturing a surface-modified fiber material of claim 10, wherein feathers, powder or microfibers using silkworm cocoons as raw materials, spun silk, wool, cotton, hemp, pulp or synthetic fibers are used as the aforementioned fiber materials. The method for manufacturing a surface-modified fiber material of claim 11, wherein feathers are used as the aforementioned fiber material. A surface-modified fiber material characterized by being manufactured by the method for manufacturing the surface-modified fiber material in any one of claims 1-12.

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