JPH03279469A - Fiber having metallic thin film and production thereof - Google Patents

Abstract

PURPOSE:To obtain a fiber material having unique metallic color tone without deteriorating the original characteristics of the fiber by metallizing a fiber material composed of natural fiber using a target consisting of a metal having getter action, thereby forming a thin film of the metal on the surface. CONSTITUTION:A fiber material having a metallic color tone and a feeling quite different from that of original natural fiber is produced without varying the characteristic features of the natural fiber by placing a fiber material composed of natural fiber in e.g. a magnetron sputtering apparatus maintained to the state of reduced pressure or vacuum and sputtering e.g. in argon while removing the gas component (e.g. water) taking advantage of the gettering action of Nb, Ti or Ta and the cooling action of a cooling panel installed in the apparatus, thereby forming a thin metal film on the surface of the fiber material.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a fibrous body having a thin metal film and a method for producing the same.

In this specification, the term "metal thin film" refers not only to a thin film made of a metal alone, but also to a thin film made of a metal compound such as a metal oxide, nitride, or carbide.

Conventional technology and its problems In recent years, preferences for textile products (threads, woven fabrics, non-woven fabrics, etc.) have increased (
Textile products are processed using various methods to respond to changes in texture, color tone, etc., and to improve properties. Particularly in the case of synthetic fibers, formation of irregular cross-sections during the spinning stage and special processing during the production of woven or non-woven fabrics are widely practiced, and greatly contribute to increasing added value.

However, in the case of natural fibers such as wool, silk, cotton, and linen, processing has not been carried out much in order to take advantage of the excellent characteristics inherent to each material. For wool, resin processing, descaling processing, plasma processing, etc., and flame retardant processing are used to impart shrink-proof properties; for silk,
Weight-increasing processing: Cotton is only subjected to flame-retardant processing, resin processing, mercer processing, etc.

However, recently, there has been a growing trend to improve the properties of natural fibers or to provide them with new properties while maintaining their original excellent properties. Therefore, attempts have been made to improve the properties of natural fibers by subjecting them to the same processing as synthetic fibers. For example, conventional synthetic fibers (polyester, polyamide,
Attempts have been made to form metal thin films using methods similar to those used for polyacrylic, etc.
In the case of natural fibers with high moisture content (wool = approximately 16%, silk =
(about 11%, cotton = about 8.5%), the gas component mainly consisting of H2O generated from natural fibers significantly increases the pressure in the vacuum chamber, impeding discharge and inhibiting thin film formation. With the technology as it is, it is virtually impossible to form a metal thin film.

As a result of intensive research in view of the current state of the technology as described above, the inventor discovered that the getter action of metal (in a vacuum state)
When subjecting natural fibers to metal vapor deposition treatment using metal as a target, a thin metal film is applied to the natural fibers while removing water by trapping by cooling and removing gaseous components mainly consisting of H2O by adsorption of metals. We have found that it is possible to form

That is, the present invention provides a fibrous body having a metal thin film and a method for producing the same as described below: (1) A fibrous body mainly made of natural fibers and characterized by having a metal thin film.

■The fibrous body, which is mainly made of natural fibers, is maintained in a reduced pressure or vacuum state, and a metal vapor deposition process is performed using a metal that has a getter action as a target, and gas components generated from the fibrous body are removed by the adsorption effect of the metal and cooling condensation. A method for manufacturing a fibrous body having a thin metal film, which comprises forming a thin metal film on the surface of the fibrous body.

The fiber body targeted by the present invention has an overall moisture content of 5.
% or more of natural fibers such as wool, silk, cotton, and hemp, and fiber bodies made of blended fibers of these natural fibers and synthetic fibers. The method of the present invention is also applicable to a fibrous body made only of synthetic fibers, but a thin metal film can be formed on a synthetic fiber body with a low moisture content by a conventional method without using the method of the present invention. The morphology of the fibrous body is filamentous,
It may be in any form such as woven fabric or non-woven fabric.

Nb is a metal having getter action.

T i, Ta5Th, V, Mo5Z r, YSS i.

An example is A12.

When forming a metal thin film, a predetermined fibrous body is placed in a thin film forming apparatus such as a sputtering apparatus, an ion blating apparatus, or a vacuum evaporation apparatus, and sputtering gas (argon or A metal thin film is formed by using a mixed gas of argon and at least one of reactive gases such as oxygen, nitrogen, acetylene, ammonia, methane, and ethylene, and targeting the metal having the above getter action. The reduced pressure condition is more preferably 10-4 to 10-1 in a high frequency sputtering device.
Approximately 3 Torr; in DC sputtering equipment, 1o-3 to 1
About 0-2 Torr; For electron cyclotron resonance sputtering equipment, about 10-4 to 10-3 Torr; For ion beam sputtering equipment, about 10"-5 to 10-3 Torr
About r; for high frequency ion brating equipment, 10
' ~10-3 Torr: For a DC ion brating device, it is ~10-2 Torr; For a vacuum evaporation device, it is about 10-6 to 10'' Torr. Among the above-mentioned thin film forming devices, the adhesion between the fibrous body and the metal thin film is good, the film thickness is easy to control, and the discharge is stable.
It is more preferable to use a sputtering device because a uniform thin film can be formed over a large area and the temperature rise of the fibrous body is small.

The thin film forming apparatus and thin film forming method used in the present invention are substantially the same as known apparatuses and methods, except that they require the use of a cooling panel, which will be described in detail below.

In the present invention, when forming a thin film, the temperature of the fiber body is set to 10
In order to maintain the temperature below 0°C to prevent deterioration of the fibrous body and to remove the gas (mainly water vapor) generated from the fibrous body by cooling and condensing, the gas from the thin film forming apparatus is
°C (vapor pressure of water at the same temperature = 10'-2 Torr
) ~-190℃ (vapor pressure of water at the same temperature = 10
A cooling panel (using liquid nitrogen, fluorocarbon gas cooled by an ultra-low temperature refrigerator, etc. as a coolant) that can cool the film to a temperature within the range of 100 to 1000 Torr is attached to the thin film forming apparatus. It can be placed near the vacuum pump in the thin film forming device, near the fibrous body, on the inner wall of the vacuum device, etc. After the fibrous body is placed in the vacuum device, the cooling panel is used for cooling only during evacuation operations and thin film formation. The gaseous components are condensed and removed by cooling the system.

On the other hand, the getter metal that has adsorbed gaseous components also adheres to the walls of the thin film forming apparatus, the sample mounting jig, etc., and exhibits the effect of removing gaseous components.

FIG. 1 shows an outline of an example of a sputtering apparatus used in carrying out the method of the present invention.

After the vacuum chamber (1) is depressurized to a predetermined degree of vacuum by an exhaust device (not shown), it is supplied with sputtering gas from the line (3) or a reactive gas from the line (5). When electric discharge is started from the power source (9) to the target metal (7) under predetermined conditions, the fibrous body (11) is sequentially sent to the supply roller (13) and the take-up roller (15). A thin metal film is formed on the surface. In the illustrated device, the cooling panel (17) is located close to the fibrous body (11).

The thickness of the metal thin film formed on the surface of the fibrous body and the raised fiber portion may be appropriately selected depending on the type of fiber and metal, the shape of the fibrous body, and the intended use, but it is usually 500 to 100 mm.
It is within the range of about 0,000 people.

The fibrous body having a metal thin film according to the present invention has a unique texture, color tone, etc. that did not exist in conventional products, so it can be used in sportswear, casual wear, formal wear, Japanese clothing, shirts, blouses, coats, etc. It is useful as a material for a wide range of clothing such as hats, gloves, bags, and shoes.

Effect of the invention According to the present invention, the following remarkable effects are achieved.

(1) A natural fiber body having a texture completely different from that of natural fibers can be obtained.

(2) Since the thickness of the metal thin film is small and is mainly formed on the raised portion, the original characteristics of the natural fiber hardly change.

(3) Natural fibers with a metallic tone (color and luster) that did not previously exist can be obtained.

(4) By combining new metallic tones with conventional dyeing methods, a greater variety of tones can be expressed.

(5) In addition, the presence of the metal thin film also achieves effects such as improved flame retardancy, antistatic properties, prevention of temperature rise due to reflection of heat rays, improved weather resistance, and improved antifouling properties.

EXAMPLES Examples will be shown below to further clarify the features of the present invention.

Experimental Examples 1 to 8 Woolen yarn 1/1 consisting of 93% wool and 7% polyamide
Woven fabric obtained using 4 (density...24 vertical pieces/
cm, 3/3 twill weave fabric (20 pieces/cm) was placed in a multi-target type DC magnetron sputtering device (manufactured by Sanyo Shinku Kogyo Co., Ltd.) with a diameter of 1.5 m and a height of 1 m. We attempted to form metal thin films using , Cu, and Ti as targets. Table 1 below shows (I) exhaust system, (
If) pumping time (min), (m) target and (IV
) Indicates the discharge status.

Table 1 Experimental examples (I) (II)
(III) (TV)I DP+M
B+RP 20 Cu Good 2 C
P+DP+MB+RP 15 Cu Good 3
DP+MB+RP 60 Cu
Defective (pressure rises significantly and discharge stops immediately) 4 CP Toko + MB + RP 25 Cu
Fairly good (pressure gradually increases and discharge becomes unstable) 5 DP Juryu + RP 20 Ti
Good 6 CP+DP+MB+RP 15 T
i Good 7 DP+MB+RP 60
Ti Slightly good (pressure rises and discharge becomes unstable) 8 CP+DP+MB+RP 25 T i
Experimental Examples 1 to 2.5 to 6 show the results when only sputtering was performed without using woolen fabric.

Furthermore, each symbol in Table 1 means the following items and conditions.

DP...Diffusion pump 26 inches Pumping speed -185
001/sec MB...Mechanical booster pump pumping speed = 1
500m3/hour RP...Rotary pump pumping speed = 35001/minC
P... Cooling panel Pumping speed = 150001/sec Pumping time... Time to reach I x 10-5 Torr Discharge status... Sputter gas = Ar, Sputter gas pressure = I x 10-3 Torr, Discharge voltage = 400
V/1 target, discharge current = A As is clear from the results shown in Table 1, by using a cooling panel and a metal such as Ti that has a getter function (experimental example Nα8), a thin metal film can be formed. The discharge for formation can be performed stably.

Example 1 Using a woolen fabric similar to that used in Experimental Example 1,
A metal thin film was formed.

First, the front side of the wool woven fabric is raised, then fluffed to even out the fuzz, washed with a petroleum-based dry cleaning solution, and washed for 10 minutes.
It was dried at 0°C for one day and night.

The wool woven fabric that had undergone the above treatment was placed in the multi-target magnetron sputtering device used in Experimental Example 1, and gas components were removed using the getter action of titanium and the cooling action of the cooling panel. Sputtering treatment was carried out under the following conditions.

Target: Ti Sputtering gas: Argon Sputtering pressure: I After smoothing out the fluff, it was dried and polished.

The color tone of the obtained fibrous body was the metallic color of titanium. In addition, the texture of the fibrous body was different from that of conventional wool woven fabrics.

Furthermore, the color fastness of the obtained fibrous bodies was measured according to the test method shown in Table 2. The results are shown in Table 3.

Example 2 A silk cloth foil of JIS L 0803 (attached white cloth for color fastness test) was sputtered and polished in the same manner as in Example 1.

The color tone of the obtained fibrous body was the metallic color of titanium. In addition, the texture of the fibrous body was different from that of conventional silk cloth.

Furthermore, various properties of the obtained fibrous bodies were measured according to the test methods shown in Table 2. The results are also shown in Table 3.

Table 2 Color fastness test items Test machine Washing JIS L 0844 A-2 method contaminated fabric Cotton Washing test machine manufactured by Kinu Suga Test Instruments Co., Ltd. L-85 Friction JIS 844 ■ Friction test machine manufactured by Suga Test Instruments Co., Ltd. ■Type FR-2 Light resistance JIS L 0842 Carbon arc lamp light
20-hour irradiation JISLO842A method contaminated cloth Cotton Kinu Suga Test Instruments Co., Ltd. Ultraviolet Long Life Fetometer FAL-5 Manufactured by Suga Test Instruments Co., Ltd. s-v First test item Washing Discoloration Fading Contamination Two-line contamination: Silk friction drying: Wet : Photoperspiric acid resistance: discoloration and fading stain; cotton stain; silk alkali: discoloration and fading stain; cotton stain; silk wool 3 to 4 4 or more 3 to 4 4 or more Examples 3 to 4 Wool similar to that used in Example 1 using woven fabric,
A titanium oxide thin film and a titanium nitride thin film were respectively formed.

First, the front side of the wool woven fabric is raised, then fluffed to even out the fuzz, washed with a petroleum-based dry cleaning solution, and washed for 10 minutes.
It was dried at 0°C for one day and night.

The wool woven fabrics treated as described above were placed in the multi-target magnetron sputtering apparatus used in Experimental Example 1, and sputtered under the following conditions.

[Example 3] Target: Ti Sputtering gas: Argon and 70% argon + 30% oxygen Sputtering pressure: IX 10-3 Torr Discharge voltage: 400V/1 target, discharge current... 3A Film thickness...Titanium - 800 people Titanium decaoxide = 700 people [
Example 4]: Target: Ti Sputtering gas: Argon and 70% argon + 30% nitrogen Sputtering pressure: I x 10-3 Torr Discharge voltage:
・400V/1 target, discharge current: 3A Film thickness: Titanium - 800 people Titanium nitride = 700 people In either case, initially, metallic titanium was sputtered in argon gas and the getter action was used. After forming a titanium film while removing gas components, sputtering was continued by adding oxygen or nitrogen to the reaction gas to form a titanium oxide film or a titanium nitride film on the titanium film.

The woolen fabric foil (Example 3) on which a titanium oxide thin film was formed had a deep blue hue, while the woolen fabric foil on which a titanium nitride thin film was formed (Example 4) had a reddish yellow hue. It was exhibiting.

Examples 5-6 Using woolen fabric similar to that used in Example 1,
A metallic zirconium thin film and a zirconium carbide thin film were respectively formed.

First, the front side of the wool woven fabric is raised, then fluffed to even out the fuzz, washed with a petroleum-based dry cleaning solution, and washed for 10 minutes.
It was dried at 0°C for one day and night.

The wool woven fabrics treated as described above were placed in the multi-target magnetron sputtering apparatus used in Experimental Example 1, and sputtered under the following conditions.

[Example 5] Target: Zirconium sputtering gas: Argon sputtering pressure: lx10 Torr discharge voltage...
400V/1 target, discharge current...3A, film thickness 800 people [Example 6]: Target...Zirconium sputtering gas...Argon and 75% argon + 25% acetylene Sputtering pressure...I x 10-3 Torr Discharge voltage...400V/1 target, discharge current...3A Film thickness...Zirconium - 800 people Zirconium carbide 1800 people In the case of Example 5, metallic zirconium was sputtered in argon gas to create a getter effect. A zirconium film was formed while removing gaseous components using the cooling effect of the cooling panel.

In the case of Example 6, metal zirconium was initially sputtered in argon gas, a zirconium film was formed while removing gas components using the getter action and the cooling action of the cooling panel, and then acetylene was added to the reaction gas. was added and sputtering was continued to form a zirconium carbide film on the zirconium film.

Wool cloth foil with metal zirconium thin film formed (Example 5)
) and woolen cloth foil with zirconium carbide thin film formed.
(Example 6) all exhibited the color of metallic zirconium.

Furthermore, the washing fastness of each of the woolen fabric foils was comparable to that of the woolen fabric foil having the titanium thin film obtained in Example 1.

Test Example I Method specified in JIS L 1091 A-1 (
The woolen fabric foil with the titanium film obtained in Example 1 was subjected to a combustion test according to the 45' microburner method). During the combustion test, heating was performed for 1 minute (however, heating was stopped after ignition of flame). Further, the flame contact surface is the titanium thin film forming surface.

The results are shown in Table 4 as samples No. 1 to 4. In addition, Table 4 shows sample N on which no metal thin film is formed.
The results for 015-7 are also shown.

Table 4 Sample Carbonization area Afterflame time Carbonization distance (C♂)
(seconds) (cm) 1 74
．． 9 107.6 20.42 70
, 2 125.2 20.43 61.
7 116.4 20.34 57.
3 106.5 20.25 Burnt down
51.2 Completely burnt down 6 Completely burned down 48.
9 Total combustion 7 Total combustion 48.0 Total combustion In the case of samples Nα1 to Nα4 according to the present invention, combustion stopped after burning up to the upper end of the holder.

On the other hand, comparative sample No. 5~ which does not have a metal thin film
In the case of 7, it was completely burnt out.

[Brief explanation of drawings]

FIG. 1 is a sectional view schematically showing an example of a thin film forming apparatus used in the method of the present invention. (1)...Vacuum chamber (3)...Inert gas supply line (5)...Reactive gas supply line (7)...Metal target (9)...Power source (11)... - Fibrous body (13)... Supply roller (15)... Take-up roller (17)... Cooling panel (and above)

Claims (2)

[Claims] (1) A fibrous body mainly made of natural fibers, characterized by having a metal thin film. (2) The fibrous body, which is mainly made of natural fibers, is maintained in a reduced pressure or vacuum state, and a metal vapor deposition process is performed using a metal that has a getter effect as a target, and the gas components generated from the fibrous body are removed by the adsorption effect of the metal and cooling condensation. A method for producing a fibrous body having a metal thin film, the method comprising: forming a metal thin film on the surface of the fibrous body.