JP3421313B2 - Antifouling fiber sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling fiber sheet which is less likely to adhere to dry dirt and oily dirt such as earth and sand, floating dust, and soot, and is easy to drop, particularly a curtain,
It is suitable for indoor and outdoor devices such as wall hangings, curtains, flags, wallpaper, fusuma paper, etc.

[0002]

2. Description of the Related Art The fibers that make up a fabric include dirt and suspended dust,
It is known to apply a gluing process to the cloth in order to make it difficult for dry dirt such as soot to adhere and to make it easier to remove the adhered dry dirt by washing, but this method is effective for cotton cloth. However, it has almost no effect on the synthetic fiber cloth which is lipophilic and tends to darken, and it requires gluing each time it is washed. Further, it is known that the cloth is treated with a mixed colloidal dispersion of silica and alumina, and the colloidal fine particles of a colorless color are used to fill the fine gaps on the fiber surface to smooth the cloth.
Although this is also effective for the cotton cloth, it is not effective for the synthetic fiber cloth, and there is a problem that the durability is poor.

On the other hand, SR processing is known as a means for preventing soiling of synthetic fiber cloth. This method, even if it is possible to prevent the deposition of oily soil to some extent, is difficult to remove once it adheres, and the inside of fibers of dry soil It had no effect on dispersion and penetration into

[0004]

DISCLOSURE OF THE INVENTION The present invention makes it difficult to adhere both dry and oily dirt such as earth and sand, floating dust, and soot to a fiber sheet such as a woven fabric, a knitted fabric, and a non-woven fabric made of synthetic fibers, and adheres the same. The above-mentioned dry stains and oily stains can be easily removed by washing, and the durability is improved without impairing the air permeability of the fiber sheet. Therefore, curtains, wall hangings, curtains, flags, wallpaper, fusuma paper, etc. Provided is a fiber sheet suitable for indoor / outdoor devices.

[0005]

The antifouling fiber sheet according to the present invention has a transparent base film made of a fluororesin on the surface of the constituent fibers of a fiber sheet made of synthetic fibers.
Impregnate or coat the fiber sheet with the oil in the form of an emulsion emulsion.
It is characterized in that it is formed by applying a cloth, drying and heat treatment, and a transparent outer coating made of ceramics containing SiO ₂ as a main component is formed by physical vapor deposition on the undercoat.

The fiber sheet used in the present invention includes nylon fiber, polyester fiber, polyacrylonitrile fiber,
It is an arbitrary fiber sheet having flexibility such as woven fabric, knitted fabric, and non-woven fabric made of synthetic fiber such as aramid fiber. It is preferably used for indoor and outdoor devices such as curtains, wall hangings, curtains, flags, wallpaper, fusuma papers, etc., which are used in an environment where dry dirt easily adheres. The fiber sheet may be plain, have a pattern pattern by dyeing or printing, or may have an emboss pattern.

In the antifouling fiber sheet of the present invention, both the front and back surfaces are coated with a transparent outer surface coating made of ceramics containing SiO ₂ as a main component. An undercoating film made of a fluororesin is formed on the surface of the fibers forming the fiber sheet. This undercoat is a fluoropolymer such as a homopolymer or copolymer of ethylene monofluoride, ethylene difluoride, ethylene trifluoride or tetrafluoride, as well as the breathable waterproofing or antifouling of knitted fabrics. The resin is impregnated or applied to the fiber sheet in the form of an emulsion emulsion, dried and heat-treated to coat the fiber, and the fiber sheet is formed to such an extent that the eyes of the fiber sheet are not blocked. The preferable thickness of this undercoat is
If it is less than 0.1 μm, it is not effective, and if it exceeds 10 μm, the transparency of the coating and the air permeability of the fiber sheet are lost, and the processing cost increases, which is uneconomical.

Then, both the front and back surfaces of the fiber sheet on which the above-mentioned base coat is formed are covered with a transparent outer coat made of ceramics containing SiO ₂ as a main component. Since this outer coating is hard, it prevents the above-mentioned dirt, suspended dust, soot and other dry dirt from invading the inside of the fiber, making it difficult to adhere, and the coating surface is hydrophilic and has excellent drop characteristics. Since the water easily flows on the surface, the attached dirt can be easily removed by washing with rain water or washing with water. The SiO _{2 which} is the main component of the ceramics is hard, but softer than other ceramics, so that it has a good compatibility with the fiber and the base film made of the fluororesin and is transparent. Therefore, the texture of the fiber sheet is not impaired.

Further, according to the present invention, since the fiber sheet is made of synthetic fiber and the above-mentioned outer coating is fixed by physical vapor deposition such as vacuum deposition, sputter deposition and ion beam method, the obtained outer coating is durable. It has excellent properties and does not fall off during use and washing. Particularly, excellent durability can be obtained by the sputter deposition and the ion beam method.
Moreover, since the undercoating film made of a fluororesin is interposed between the synthetic fibers constituting the fiber sheet and the outer coating, the peeling resistance of the outer coating is higher than that in the case where the outer coating is directly formed on the surface of the synthetic fiber. It is remarkably improved, oil stains and dry stains are less likely to adhere, and the adhered stains are easily removed.

When the fiber sheet is cooled from the opposite side during sputter deposition to quench the deposit, the outer coating does not have a crystalline structure but has an amorphous structure and a dense aggregate of extremely fine needle-shaped bodies. Therefore, the texture of the fiber sheet is maintained without touching the film, and the needle-like body is not peeled off even when the fibers constituting the fiber sheet are bent, and the durability is further improved.

The above-mentioned outer surface coating may be formed only of SiO _2, but if it is a ceramic containing SiO ₂ as a main component, other ceramics may be contained within the range not impairing the object of the present invention. it can. For example, a ceramic containing SiO ₂ as a main component and Sn O ₂ as an auxiliary component facilitates sputter deposition, and since Sn O ₂ is hard, the antifouling property against dry stain is improved. And SiO ₂ and Sn
Since the outer surface coating made of O ₂ is excellent in hydrophilicity and drop characteristics, water easily flows on the surface and stain removal is improved. Also, the outer surface coating, the main component Si O _2, Sn O
_When formed of ceramics containing ₂ and Zn ₂ O 3 as auxiliary components, since Zn 2 O 5 has conductivity, it is effective in preventing dirt adhesion due to static electricity.

[0012] an outer surface coating of Si O ₂ described above, that a plate made of silicon to the target of the sputtering apparatus, and sputtering in an atmosphere containing a trace amount of oxygen, is adhered to the surface of the fiber sheet while oxidizing silicon Easily obtained by. The outer surface coating composed of SiO ₂ and Sn O ₂ can be obtained by sputtering in the same manner as above using a sintered plate of a mixed powder of silicon and tin as a target. The outer coating made of SiO ₂ , Sn O ₂ and Zn O targets a sintered plate of silicon, tin and zinc, or a mixed arrangement of the sintered plate of silicon and tin and the zinc plate. It is obtained by using a target and performing sputtering in the same manner as above.

The thickness of the outer coating is 1 to 200 n.
m is preferable, and if it is less than 1 nm, the effect as an outer coating cannot be obtained, and the durability becomes poor.
When it exceeds, the texture of the fiber sheet is lost, the transparency is lowered, and the pattern on the fiber sheet becomes difficult to see, which is not preferable.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In FIG. 1, reference numeral 10 denotes an antifouling fiber sheet according to the present invention, which includes a warp yarn 11a and a weft yarn 1
1b is a fiber sheet 11 suitable for indoor / outdoor devices such as curtain fabrics woven using multifilament yarn or spun yarn made of synthetic fiber such as polyester fiber, and the surface of the warp yarn 11a and the weft yarn 11b. It is composed of an undercoat 12 and an outer coating 13 covering the undercoat 12.

The above fiber sheet 11 is woven and refined,
After applying the set, dyeing, drying and heat setting,
The undercoat 12 is formed by immersing in an emulsion emulsion containing fine powder of tetrafluoroethylene resin and initial condensate of melamine resin, squeezing with a mangle to dry, and heat setting. The thickness of the base coating 12 is 0.1 to 10 μm which does not impair the air permeability of the fiber sheet 11.
set to m.

Then, on the undercoat 12, SiO ₂
Is formed as a main component in a thickness of 1 to 200 nm. The outer coating 13 is preferably formed by sputtering. That is, the fiber sheet 11 having the above-mentioned base coating 12, that is, the fiber sheet 11A with the base coating is spread and placed in a closed chamber,
The anode and the target are arranged so as to face the surface so that the anode is located between the fiber sheet 11A with the undercoat and the target, and sputtering is performed under a vacuum by applying a high voltage between the anode and the target.

FIG. 2 shows a two-stage type sputtering apparatus in which two sets of vapor deposition apparatuses are arranged side by side in the above-mentioned closed chamber. In FIG. 2, reference numeral 20 denotes a closed chamber, and the first water-cooled cylinder 21 and the second water-cooled cylinder 2 are provided on the left and right of the central portion.
2 are arranged side by side, and the first water cooling cylinder 21 on the left side rotates in the counterclockwise direction and the second water cooling cylinder 22 on the right side rotates in the clockwise direction.

The delivery shaft 23 of the fiber sheet 11A with the underlying coating is provided above the first water-cooled cylinder 21, and the processed fiber sheet, that is, the soil-resistant fiber sheet 10 is provided above the second water-cooled cylinder 22. Each of the winding shafts 24 is rotatably installed. The fiber sheet with an undercoating 11A pulled out from the delivery shaft 23 is wound around the first water-cooling cylinder 21 via the first guide roller 25a so that the back surface of the fiber sheet with an undercoating film 11A contacts. The first water cooling cylinder 21 is separated from the first water cooling cylinder 21 via the second guide roller 25b, and the upper third guide roller 25
c, so that the surface of the fiber sheet 11A with the undercoat is brought into contact with the second water-cooled cylinder 22 by being guided by the fourth guide roller 25d on the upper right, passing over the delivery shaft 23, and passing through the fifth guide roller 25e on the lower side. The second water-cooled cylinder 22 is separated from the second water-cooled cylinder 22 through the sixth guide roller 25f, and is taken up by the winding shaft 24.

The above-mentioned first water-cooled cylinder 21 and second
Below the water-cooled cylinder 22, a pair of left and right first and second anodes 27 and 28 are installed.
Then, a water-cooled first target source 29 and a second target source 30 are installed below the first anode 27 and the second anode 28, respectively, and silicon is placed on the first target source 29 and the second target source 30. The flat plate-shaped targets 31 are fixed, respectively, and are arranged between the first anode 27 and the first target source 29 and between the second anode 28 and the second target source 30.
A DC power source E having a voltage of 200 to 1000 V is interposed between the two.

In the above structure, the delivery shaft 23, the take-up shaft 24 and the water cooling cylinders 21 and 22 are rotated, and the fiber sheet 11A with the undercoat is delivered from the delivery shaft 23 at a predetermined speed. 21 and the second water-cooled cylinder 22 in order and while being taken up by the take-up shaft 24, the first water-cooled cylinder 21 cools the above-mentioned fibrous sheet 11A with an undercoat from the back side, and the second water-cooled cylinder 22 uses the above-mentioned fibrous sheet 11A. Fiber sheet with undercoat 11A
Is cooled from the front side. On the other hand, the vacuum pump (not shown) connected to the closed chamber 20 is driven to reduce the internal pressure of the closed chamber 20 to about 1.3 × 10 ⁻³ Pa, and then the gas cylinder (not shown). Argon gas is introduced into the chamber 20 to adjust the internal pressure of the closed chamber 20 to about 6.6 × 10 ^-2 Pa, and oxygen is introduced from an oxygen cylinder (not shown) into the chamber 20.
Adjust the internal pressure to about 2.6 × 10 ^-1 Pa.

Next, a direct current voltage is applied between the first anode 27 and the first target source 29 to cause the silicon in the flat target 31 to fly out and react with oxygen in the closed chamber 20 to form an oxide. Then, these are adhered to the surface of the fibrous sheet 11A with a base coating on the first water-cooled cylinder 21 and rapidly cooled to form an outer coating 13 (see FIG. 1) having an amorphous structure. At this time, the thickness of the outer coating 13 is formed to 1 to 200 nm by adjusting the feed speed of the fiber sheet 11A with the undercoat.

In this way, the sputtering in the first water-cooled cylinder 21 proceeds, and the intermediate product consisting of the fiber sheet 11A with the undercoat and the outer coating 13 on the front side becomes the second product.
When the water-cooled cylinder 22 is reached, a DC voltage is applied between the second anode 28 and the second target source 30 to eject silicon from the flat target 31 in the same manner as described above. The reaction is performed to form an oxide, and these are attached to the back surface of the fiber sheet 11A with an undercoat in the same manner as above, and rapidly cooled to form an outer coating 13 (see FIG. 1) having an amorphous structure with a thickness of 1 to 200.
nm. Then, when the entire fibrous sheet with an undercoating film 11A wound around the delivery shaft 23 is completely transferred to the take-up shaft 24, the atmosphere is introduced into the closed chamber 20 and the fibrous sheet with an undercoat film 11A is introduced from the closed chamber 20. 1-200 nm thick outer coating 1 on both front and back
The antifouling fiber sheet 10 provided with No. 3 is taken out.

In the above embodiment, the water-cooled cylinders 21, 22 and the anodes 27, 2 are provided in one closed chamber 20.
8 and target source 29, 30
Forming a set, forming the outer coating 13 on the front surface with the first vapor deposition device and subsequently forming the outer coating 13 on the back surface with the second vapor deposition device while spreading and transferring the above-mentioned fiber sheet 11A with the base coating. However, one set of vapor deposition apparatus is installed in the closed chamber, and after forming the outer coating 13 made of SiO _{2 on} the surface of the fiber sheet 11A with the undercoat, the fiber sheet 11A with the undercoat is taken out. Then, it is also possible to turn over the fibrous sheet 11A with the underlying coating, mount it again in the closed chamber, form the outer coating 13 on the back surface, and take out the antifouling fibrous sheet 10. However, when the apparatus shown in FIG. 2 is used, the time and effort required for attaching and detaching the fiber sheet 11A with the undercoat to the closed chamber and reducing the pressure in the chamber are reduced by half.

In the above embodiment, the target 27
Is made of silicon to form the outer surface coating 13 composed of only SiO _2, but a sintered plate in which silicon and tin are mixed in a ratio of 9/1 to 6/4 is used as the target 27. Other than the above, by sputtering in the same manner as described above, the outer surface coating 13 containing SiO ₂ as a main component and Sn O ₂ as an accessory component is obtained, which facilitates vapor deposition and improves antifouling property against dry stain. . Further, by sputtering in the same manner described above and substituting zinc 10 to 50% by weight of tin constituting the target 27, the Si O ₂ as a main component, the outer surface coating 13 of a SnO ₂ and Zn O and subcomponent Is obtained, and the antifouling property against electrostatic stain is improved.

[0025]

EXAMPLE A 30-count spun yarn made of polyethylene terephthalate fiber was used for the warp 11a and the weft 11b, and the warp density and the weft density were both 80 yarns / inch (31.5 yarns / c).
m) plain weave (fiber sheet 11) was woven, and sodium carbonate (2 g / l) and nonionic surfactant (5 g /
l, "Score Roll 900" manufactured by Kao Corporation,
Refining was carried out with a jet dyeing machine at a bath ratio of 1:20 at 100 ° C for 20 minutes, followed by thorough washing with water and drying, followed by heat setting at 180 ° C for 60 seconds.

Next, the refined fiber sheet 11 is dipped in a 2% aqueous solution of a fluorine-based water repellent (“Asahi Guard AG925” manufactured by Asahi Glass Co., Ltd.), squeezed to a squeezing ratio of 70% with a mangle, dried and heat treated. 170 ° C x 6
The operation was performed for 0 seconds to form an undercoat film 12 having a thickness of 0.5 μm on the fiber sheet 11.

Subsequently, the obtained fiber sheet 11A with an undercoat is attached to the delivery shaft 23 of the sputtering apparatus of FIG. 2, and a sintered plate in which silicon and tin are mixed in a ratio of 7/3 is used as a target 31. Sputter vapor deposition is performed to form an outer surface coating 13 having a thickness of 5 nm in which SiO ₂ and Sn O ₂ are mixed in a ratio of 7/3 on both front and back surfaces of the above-mentioned fiber sheet 11A with an undercoat, and the antifouling fiber of the example. Sheet 10 was obtained.

Comparative Example 1 The plain weave (fiber sheet 11) used in the above examples was refined in the same manner as in the examples, washed with water, dried and heat set.
By omitting the subsequent processing, the above-mentioned undercoat 12
A fiber sheet of Comparative Example 1 having neither the outer coating 13 nor the outer coating 13 was obtained.

Comparative Example 2 A fibrous sheet of Comparative Example 2 having the same underlying coating 12 as that of Example but no outer coating, except that the sputter deposition was omitted in the above example. Obtained.

Comparative Example 3 The fiber sheet 1 after refining was carried out in the same manner as in the above example except that the step of forming the undercoat 12 was omitted.
An antifouling fiber sheet of Comparative Example 3 was manufactured by directly forming an outer surface coating 13 made of the above 7/3 mixture of SiO ₂ and Sn O _{2 on} 1.

The fiber sheets of the above-mentioned Examples, Comparative Examples 1, 2 and 3 were subjected to a stain treatment and a washing treatment according to JIS L.
0844 A-2 (laundry method) was applied according to each light reflectance before, after and after cleaning (wavelength of light used: 51
7 nm) was measured to compare the antifouling properties. Contaminants consist of stearic acid, oleic acid, hardened oil and olive oil 12.5% each, cetyl alcohol 8.5%, solid paraffin 21.5%, cholesterol 5.0% and carbon black 15.0%. Oil-based pollutants, clay 55.0%, Portland cement 17.0%, silica gel 17.0%, ferric oxide 0.5%, n-decane 8.
A mixture of a dry contaminant consisting of 75% and 1.75% carbon black in a ratio of 3/1 was used. The results are shown in Table 1 below.

[0032]

[Table 1] In Table 1, when the reflectance before contamination is a, the reflectance after contamination is b, and the reflectance after cleaning is c, the contamination rate is expressed by the formula [contamination rate = (ab) / a × 100]. Be done. The cleaning rate is calculated by the formula [cleaning rate = (c−b) / (ab) × 100].
It is represented by.

As is clear from Table 1 above, when the mixture of the oily and dry pollutants was used as the pollutant, the examples were the least stain resistant and the best stain remover. In addition, the fiber sheets of Comparative Examples 1 to 3 and Examples described above,
Almost no difference in appearance and touch was observed, but when each was hung outdoors for one month and visually inspected for dirt in the open air, Example and Comparative Example 3 were compared with Comparative Examples 1 and 2. Obviously, the amount of stains was small, and the stains were removed quickly when washed with a home washing machine, and the number of stains after 5 times of washing was almost the same as at the beginning. Immediately after trial production of the above-mentioned Example and Comparative Example 3, a commercially available packing gum tape was attached to the outer surface coating and a peeling test was conducted. No peeling of the outer surface coating was observed.

[0034]

As described above, since the antifouling fiber sheet of the present invention has an antifouling function against dry dirt,
Difficult to stain against both dry and oily stains,
Moreover, even if it adheres, it can be easily dropped and has excellent durability. And since it is transparent, the color and pattern of the fiber sheet can be seen from the outer surface coating, and the texture is almost the same as that without the outer surface coating, and it is suitable for indoor and outdoor devices that easily get dry stains. . Moreover, since the undercoating film made of a fluororesin is interposed between the fiber sheet and the outer coating, the antifouling performance and the peeling strength of the outer coating are significantly improved. Particularly, in the invention according to claim 2, the antifouling property against dry dirt is further improved. Further, claim 3
The invention according to (1) has improved antifouling property against static electricity stains.

[Brief description of drawings]

1 is a cross-sectional view of an embodiment of the invention.

FIG. 2 is a sectional view showing an example of a sputtering apparatus.

[Explanation of symbols]

10: Antifouling fiber sheet 11: Fiber sheet 11a: warp 11b: weft 11A: Fiber sheet with undercoat 12: Undercoat 13: Outer coating

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eigo Nakajima 36 Hama-cho, Gamagori-shi, Aichi Prefecture Suzu-Tora Co., Ltd. (56) References JP-A-60-134068 (JP, A) Actual exploitation Sho-62-176358 (JP) , U) International publication 96/023910 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) D06M 11/00-15/72

Claims (3)

(57) [Claims] 1. A transparent undercoating film made of a fluororesin is provided on the surface of the constituent fibers of a fiber sheet made of synthetic fibers.
Impregnate or coat the fiber sheet with the oil in the form of an emulsion emulsion.
Antifouling property, which is formed by applying a cloth, drying, and heat treatment, and a transparent outer surface film made of ceramics containing SiO ₂ as a main component is formed on the undercoating film by physical vapor deposition. Fiber sheet. 2. The outer coating mainly comprises SiO ₂ and Sn
A ceramic material containing O ₂ as an accessory component.
The antifouling fiber sheet described. 3. The outer coating mainly comprises SiO ₂ and Sn
The antifouling fiber sheet according to claim 1, which is formed of a ceramic containing O ₂ and Zn O as subcomponents.