JPH03287863A - Fiber having interference color and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject fiber useful as a clothing material by forming a thin metal film layer and a transparent metal compound thin film layer on a fiber in order for coloration to what is called iridescence color without deterioration of touch, etc., of the fiber material itself. CONSTITUTION:A fiber is subjected to thin metal film layer formation treatment in the presence of an inert gas or without using the gas while holding the fiber in a reduced pressure or vacuum state. Metal compound thin film layer formation treatment is then carried out in the presence of an inert gas containing metal compound-forming components, thus obtaining the objective fiber having a thin metal film layer and a transparent metal compound thin film layer formed thereon in order. In addition, Al, Cr, etc., and TiO2, In2O3-SnO2, etc., are suitably used respectively as the metal for the thin metal film layer and as the metal compound for the metal compound thin film layer.

Description

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

Conventionally, in order to impart color to fibers, methods such as dyeing with inorganic or organic dyes and fixing pigments on the surface or inside of the fibers have been widely adopted.

Incidentally, in recent years, in order to respond to changes in preferences for fibrous bodies (threads, woven fabrics, non-woven fabrics, etc.), methods of imparting colors to fibrous bodies by means other than dyeing have been proposed.

(b) For example, Japanese Patent Application Laid-open No. 59-228042 states,
Two or more types of polymers with different shrinkage characteristics are laminated together in the axial direction to form a linear flat composite fiber, and the fiber has at least four convex portions on both sides in the length direction of the fiber cross section. 30% of such fiber is
The above discloses a woven fabric containing a scale structure that stands up at an angle of 45 degrees or more with respect to the woven fabric surface on the fiber surface.

This textile is intended to produce an elegant color effect similar to that seen on butterfly wings.

However, this method has a complicated structure and manufacturing process, and also requires the use of conventional dyeing methods in order to significantly change the hue and obtain vivid colors.

(b) Furthermore, JP-A-60-134068 discloses a method for obtaining a fibrous body with bright colors and improved color depth by depositing a transparent inorganic oxide by sputtering. There is. However, this method has a problem in that the fibrous body dyed by the conventional dyeing method loses its original hue due to the formation of an inorganic oxide layer.

(c) JP-A-62-17051 discloses a fiber in which a number of slits having a specific width are provided at specific intervals on the fiber surface in the fiber axis direction, and the fiber has an interference color. There is.

The fibers disclosed herein also have a complicated structure and manufacturing process, and in order to greatly change the hue and obtain vivid colors, conventional dyeing methods must be used in combination.

Means for Solving the Problems As a result of intensive research in view of the current state of the technology as described above, the present inventor has found that when a thin metal film layer and a transparent metal compound layer are sequentially formed on the surface of a fibrous body, It was discovered that a fibrous body exhibiting vivid coloring due to interference colors can be obtained without using any dyes.

That is, the present invention provides the following fibrous body and method for producing the same: ■ A fiber having an interference color characterized by sequentially comprising a metal thin film layer and a light-transmitting metal compound thin film layer. body.

■Maintaining the fibrous body in a reduced pressure or vacuum state and performing metal thin film layer formation treatment in the presence or absence of an inert gas,
Production of a fibrous body having an interference color and comprising a metal thin film layer and a light-transmissive metal compound thin film layer, which is then subjected to a metal compound thin film layer forming treatment in the presence of an inert gas containing a metal compound forming component. Method.

Hereinafter, the fibrous body, metal thin film layer, and metal compound thin film layer used in the present invention will be explained in detail.

1. m-pyramid The fiber body targeted by the present invention has an overall moisture content of 5
% or less, and there are no particular restrictions on the material, form, etc., as long as there is little degassing under reduced pressure or vacuum conditions. Materials with a high moisture content (such as natural fibers) may be used after reducing the moisture content to 5% or less by drying or other means.

More specifically, fibers include synthetic fibers such as polyester, polyamide, polyacrylic, acetate, vinylon, polypropylene, and rayon; natural fibers such as wool, silk, cotton, and hemp; and inorganic fibers such as glass fiber and carbon fiber. Class: Examples include blended fibers of the above-mentioned natural fibers and synthetic fibers. Among these fibers, synthetic fibers with low water content are more suitable. The form of the fibrous body is filamentous, woven,
It may be in any form such as non-woven fabric.

(2) Metal thin film layer The metal applied as a thin film layer (hereinafter referred to as the first layer) on the surface of the fiber body is A1, Cr5Ti.

Au5Cu, , Mo5Nb, W, Fe, Ni, Co.

Examples include Ta. Thin film layer metals may be selected according to various criteria, such as:

(a) To increase the brightness, metals with high reflectance (A1
etc.). However, since A1 has a low complex refractive index, the color becomes lighter.

(b) In order to exhibit various hues, it is sufficient to use metals (Cr, Ti, etc.) that have flat reflectance in the visible region.

(C) In order to limit the color to a certain hue, a colored metal (Au, Cu, etc.) having specific absorption or reflection in the visible region may be used.

In particular, in order to obtain bright colors with a wide range of hues, Ti, M
o, Nb5W, Fe, Cr, Ni, C.

etc. are suitable.

The thickness of the metal thin film layer, which is the first layer, may be selected appropriately depending on the type of fiber and metal, the shape and purpose of the fiber body, the desired color tone, etc., but it is usually within the range of about 100 to 3000. Yes, more preferably 500 to 2000
It is within the range of about Å.

(2) Metal Compound Thin Film Layer The metal compound applied as the second layer on the metal thin film layer is preferably one having a transmittance in the visible region of 50% or more and a refractive index in the range of 1 to 4. Such metal compounds include TiO2, In203-8n02,
Oxides such as S 1OSS i02, Al2O3, Ta205; AQN.

Nitride such as Si3N4, BN; Carbide such as SiC;
Examples include fluorides such as MgF2 and LiF. Although diamond does not belong to metal compounds, it has a refractive index of 2.
．． 4 and has excellent transparency, abrasion resistance, corrosion resistance, etc., so it is useful as a second thin film layer. Among these transparent metal compounds, Ti has a high refractive index of about 2.2 to 2.7, excellent wear resistance, and is chemically stable.
O2 is particularly preferred.

The thickness of the metal compound thin film layer, which is the second layer, is determined as appropriate depending on the type of metal forming the first layer and the metal compound forming the second layer, the type, shape and use of the fiber body, the desired color tone, etc. You can choose the number of people, but it is usually within the range of 100 to 10,000 people, more preferably 300 to 7,000 people.
It is within the human range.

The method of the present invention is generally carried out as follows. First, a predetermined fibrous body is placed in a known thin film forming device such as a sputtering device, an ion blating device, a vacuum evaporation device, etc., and a metal thin film layer that will become the second layer is placed under a reduced pressure of about 10-6 to 10-2 Torr. formation. Next, a metal compound thin film layer is formed by the same operation. More specifically, when using a sputtering device or an ion blating device, after forming a metal thin film layer by sputtering or vapor deposition while introducing argon gas, argon gas and metal compound forming components (oxygen, nitrogen, A metal compound thin film layer is formed by sputtering or vapor deposition while introducing a mixed gas with acetylene, fluorine, etc.). Alternatively, after forming a metal thin film layer using a vacuum evaporation apparatus, a sputtering apparatus or an ion blating apparatus may be used to form a metal compound thin film layer in the same manner as described above. It goes without saying that the metal species used to form the first layer and the metal species used to form the second layer may be the same or different.

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 device was heated to -50°C.
It is preferable that a cooling panel (using liquid nitrogen, for example, as a coolant) that can be cooled to a temperature in the range of -190°C is installed in the thin film forming apparatus. The thin film forming apparatus and thin film forming method used in the present invention are not substantially different from known apparatuses and methods.

In the fiber body according to the present invention, it has been confirmed by a scanning electron microscope that the thickness distribution of the thin film layer formed on the yarn surface is non-uniform. It is presumed that the non-uniformity of the thickness of this thin film layer is the cause of the appearance of different hues depending on the viewing angle (so-called "iridescent" appearance).

In this way, the fibrous body of the present invention, which has an interference color due to the metal thin film, has a unique color tone that did not exist in conventional products, so it can be used in sportswear, casual wear, formal wear, stage wear, Japanese clothing, etc. It is extremely useful as a material for a wide range of clothing such as clothing, shirts, blouses, tights, pantyhose, coats, hats, gloves, bags, and shoes, as well as as decorative materials and construction materials.

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

(1) Since the thickness of the entire thin film layer is thin, there is almost no change in the properties of the fiber material itself, such as texture, air permeability, and moisture permeability.

(2) It produces a so-called "iridescent" coloration that appears to be a different color depending on the viewing angle.

(3) By controlling the thickness of the metal compound layer, any desired pattern, design, etc. can be created.

(4) The presence of the metal thin film layer 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.

Example 1 Woven fabric made of vertical polyester 75D/36f and horizontal polyester 100D/48f (density...vertical = 4
9.6 lines/cm, width = 33.8 lines/cm, weight = 1
10g/r+f3/oblique weave cloth foil: below fibrous body (1)
), JIS L ○803 (attached white polyester cloth foil for color fastness test (hereinafter referred to as fiber body (2)) and two-way tricot (material for swimwear)
28 gauge, nylon 40d-polyurethane 40d:
The fiber body (hereinafter referred to as (3)) 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, and Ti was used as the target under the following conditions. A metallic titanium thin film layer (800 pieces) and a titanium oxide thin film layer (2000 pieces) were formed.

[Layer-1 = titanium metal thin film layer formation conditions co-sputter gas
...Argon sputtering pressure...I
...Argon 70% 10 oxygen 30% sputtering pressure...I
X 10-3 Torr Discharge voltage: 400 V/1 Target discharge current: 3 A The three types of thin film layer-forming fibers obtained had a yellowish green color tone. Furthermore, the texture of the thin film layer-formed fiber body was almost the same as that of the original fiber body.

The color fastness of the obtained fibrous bodies was measured according to the test method shown in Table 1. The results are shown in Table 2.

As is clear from the results shown in Table 2, although the product of the present invention has slightly low fastness to friction, it is excellent in other fastness properties.

Table 1 Dyeing fastness test items Test method Test machine washing JIS L 0844 A-2 method Suga Test Machine Co., Ltd. Ribata dyed fabric Cotton Silk Washing test machine LM-85 friction JIS L 0844 Type II Suga test machine (
Co., Ltd. Friction Testing Machine Type FR-2 Irradiation JIS L 0842 Carbon arc lamp light 20 hours irradiation Suga Testing Machine Co., Ltd. i outside! Long Life Fetometer FAL-5 Sweat JIS L 0842 Method A contaminated cloth Cotton s-v manufactured by Kinusuga Test Instruments Co., Ltd. Test items: Washing discoloration/fading contamination: Cotton contamination: Silk friction drying: Wet: Sweat by sunlight Table 2 11 bodies (1) 11 bodies (2> 11 bodies (3) 3
~43~43~4 3 3 3 4 or more 4 or more 4 or more Acid: Discoloration and fading stain; Cotton stain: Silk alkali: Discoloration and fading stain; Cotton stain; Silk Example 2 The same fibrous body as used in Example 1 ( 1) and fibrous body (2) in the same manner as in Example 1.
After forming the layer, a titanium oxide layer having a different thickness was formed as a second layer in the same manner as in Example 1 except that the sputtering treatment time was changed.

FIG. 1 shows the relationship between titanium oxide film thickness and hue.

In Fig. 1, each point indicated as . is the result for the fiber body (1), and each point indicated as ○ is the result for the fiber body (2).
).

Color was measured using a multi-light source spectrophotometer (“MSC-2” manufactured by Zuga Test Instruments Co., Ltd.; the light source was C light source, and a 2-degree field of view was used).
Measured by CIE (Commission Internationale de l'Eclairage) - L'a
Displayed using the 'b' color system.

In addition, L'a' and b' are tristimulus values X, YSZ
It was calculated from the value using the formula below.

L' = 116 (Y/YO') 17'3-16a'
=50(H(X/Xo)"3-(¥/Yo)"3
]b'=2QO[(Y/Yo)"3-(Z
/ Zo) ”” EHere, x = X / (X
+ Y + Z), Y = Y/ (X+Y+Z)
, z-Z/ (X+Y+Z), then x-+-y+
z=1 Constant (tristimulus value of C light source): Xo =98.00
, Yo = 100.00 Z o = 118.22 As is clear from FIG. 1, various hues can be expressed by changing the thickness of the titanium oxide film. In addition, even if the thickness of the titanium oxide film is the same, the shape of the fiber (
By changing the shape, weaving method, etc.), the color difference changes, so the color can be changed.

Example 3 In order to clarify the relationship between the film thickness of the second layer and the interference color,
A titanium thin film layer (film thickness = 800 Å) as a first layer and a titanium oxide thin film layer (film thickness = 200 to 230 OA) as a second layer were deposited on a 14 mm x 17 mm glass substrate using an ion beam sputtering apparatus (Japan) under the following conditions. (manufactured by Vacuum Technology Co., Ltd.).

[Titanium thin film layer formation conditions] Target: Titanium sputtering gas: Argon sputtering pressure: 8 x 10” Torr ion source: Acceleration voltage: 1500V Extraction voltage: 300cm Discharge current: 3A Ion beam current...70mA [Titanium oxide thin film layer formation conditions] Target...Titanium sputtering gas...Argon + oxygen sputtering pressure...Total pressure 1.3 x 10-'
Torr (Argon partial pressure 8 x 10-5 Torr Oxygen partial pressure 5 x 10-5 Torr Table Ion source: Acceleration voltage...1000V Extraction voltage...300V Discharge current...3A Ion beam current...74-78mA Table 3 shows the relationship between the film thickness of titanium oxide and the interference color produced.

Film thickness (in) 00 00 500-700 700-800 200 400 500 700 800 2000-2100 200 300 Interference color Dark yellow Dark purple Blue Light blue Yellow Pink Purple Purple Blue Green Blue Yellow Green Green Yellow Light yellow Results shown in Table 3 It is clear from the above that by varying the thickness of the titanium oxide film at intervals of about 100 units, various hues can be obtained without using dyes or pigments.

Example 4 In order to clarify the relationship in optical properties between the metal thin film layer serving as the -th layer and the transparent metal compound layer serving as the second layer, the metal thin film layer (100 pieces) as the -th layer and the second A titanium oxide thin film layer was formed using a magnetron sputtering device (manufactured by Riken Co., Ltd.) under the following conditions, and the titanium oxide thin film layer was formed using a spectrophotometer (
(manufactured by Shimadzu Corporation), the reflectance of each was measured.

[Metal thin film layer forming conditions]: Target...Predetermined metal sputtering gas...Argon sputtering pressure...6 x 10-3 TorrRF power...500W [Titanium oxide thin film layer forming conditions]: Target...Titanium Sputtering gas...Argon + oxygen sputtering pressure...Total pressure 6 x 10-3To
rr (Argon partial pressure 5 X 10-3 Torr Oxygen partial pressure I The contents are as follows.

*Figure 2 shows the reflection spectrum of the metal thin film itself formed on the glass plate.

Note that, for reference, FIG. 2 also shows the reflection spectrum of the Si substrate itself.

*Figure 3 shows the reflection spectrum of titanium oxide thin film layer/titanium thin film layer.

*Figure 4 shows the reflection spectrum of titanium oxide thin film layer/platinum thin film layer.

*Figure 5 shows the reflection vector of the titanium oxide thin film layer/gold thin film layer.

*Figure 6 shows the reflection spectrum of titanium oxide thin film layer/chromium thin film layer.

*Figure 7 shows the reflection spectrum of titanium oxide thin film layer/Si substrate.

The numerical values in FIGS. 3 to 7 indicate the film thickness of titanium oxide.

As is clear from the results shown in FIGS. 3 to 7, in both cases, spectra due to interference are observed due to the increase in the thickness of the titanium oxide film.

Furthermore, changing the type of metal constituting the second layer also changes the spectrum, causing a change in color.

Example 5 Using the same fibrous body (2) as used in Example 1,
An AQ metal thin film layer (1000 Å) as the first layer and a transparent AQN thin film layer (3000 Å) as the second layer were formed using a magnetron sputtering device (manufactured by Riken Co., Ltd.) under the following conditions. The reflectance of each was measured using a multi-light source spectrophotometer (“MSC-2 type” manufactured by Zuga Test Instruments Co., Ltd.; the light source was a C light source, and a 2-degree field of view was used).

[1 thin film layer formation conditions: Target...AQ Sputtering gas...Argon sputtering pressure...6 x 10-3 TorrRF power...300W [ARN thin film layer formation conditions: Target...AQ Sputtering gas ...Argon denitrogen sputtering pressure...Total pressure 6 x 10-3To
rr (Argon partial pressure 3.4 x 10””Torr Nitrogen partial pressure 1.3 x 1O-3TorrRF power...30
0W Film thickness: The reflectance in the range visible to 500 to 2,700 people is shown as a curve (A) in FIG. Note that the curve (Ao) shows the reflectance of the polyester cloth foil on which no thin film is formed.

In the product of this example, the reflectance increases on the long wavelength side and decreases on the short wavelength side. In addition, HVC value (Hue 5Val
ue and Chroma) is 1.63YR.

6.68.2.30, and it can be seen that it is colored yellow.

Example 6 Example 1 was applied onto the same fibrous body (2) as used in Example 1.
A metallic titanium thin film (film thickness = 800 Å) was formed in the same manner as above, and then a transparent SiO2 thin film layer (film thickness = 1250 Å) or MgF was formed using an electron beam evaporator.
Two thin film layers (thickness = 3000 layers) were formed.

Next, a multi-light source spectrophotometer (“MSC-2 type” manufactured by Zuga Test Instruments Co., Ltd.; the light source was a C light source, and a 2-degree field of view was used)
The reflectance of each cloth was measured.

The results are shown in Fig. 9 as the northern latitude (B) (S i O2 thin film layer formed product) and in Fig. 10 as the curve (C) (MgF
(2 thin film layer formed product) as shown. In addition, the curve (B")
and the curve (Co) show the reflectance of the polyester fabric (without forming a thin film), respectively.

The IVC value of the 5in2 thin film layer type product is (2,28PB
, 4.44.5.79), and the hue was yellow.

In addition, the HVC value of the MgF2 thin film layer formed product is (9,97
YR, 4,61,2,95), and the hue was blue.

Example 7 A tantalum metal thin film (film thickness = 800 layers) was formed on acrylic, acetate, and rayon cloth of JIS L 0803 (attached white cloth for color fastness test) under the following conditions, and then ion beam was applied on top of it. A transparent Ta205 thin film layer (thickness=2500 or 3000 Å) was formed using a grasshopper apparatus.

[Layer-th layer=Metal tantalum thin film layer formation conditions]: Target: Tantalum sputtering gas: Argon sputtering pressure: IX 10-5 Torr Ion source acceleration voltage: 1500V Extraction voltage: 300V Discharge current ...3A Ion beam current...70mA Second layer = tantalum oxide thin film layer formation conditions]: Target...Tantalum sputtering gas...Argon + oxygen sputtering pressure...Total pressure I X 10-'To
rr Argon partial pressure...8x1O-5Torr Oxygen partial pressure -5X 10''Torr Ion source acceleration voltage...100OV Extraction voltage...300V Discharge current...3A Ion beam current...74 to 77mA The film interference color obtained on the fibers was the same for all fibers, and was pink when the tantalum oxide thin film layer thickness was 2500 Å, and blue-green when the tantalum oxide thin film layer thickness was 3500 Å. Further, the washing fastness was almost the same as in Example 1.

Example 8 Glass fiber cloth foils measuring 13 pieces/cm vertically and 16 pieces/cm horizontally were used under the following conditions using a multi-target type magnetron sputtering device (manufactured by Sanyo Shinku Kogyo Co., Ltd.). Sputtering was performed.

[Titanium thin film layer formation conditions: Target...Titanium sputtering gas...Argon sputtering pressure...8 x 10'-4 Torr Applied voltage...400/Target film thickness...800Å [Titanium oxide thin film layer formation] Conditions Cotarget: Titanium sputtering gas: 70% argon, 30% oxygen Sputtering pressure: 8 x 10-4 Torr Applied voltage:
400/Target film thickness...2000 The obtained fibers had a yellowish green color.

Example 9 JIS L 0803 (attached white cloth silk foil for color fastness test) 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. Using Ti as a target, a metallic titanium thin film layer (800 Å) and a titanium oxide thin film layer (2000 Å) were formed under the following conditions.

[Second layer = titanium metal thin film layer formation conditions] Varnish sputtering gas...Argon sputtering pressure...I x 10-4Torr Discharge voltage...400V/1 target discharge current...3A [Second layer - titanium oxide thin film Layer formation conditions] Varnish sputtering gas: 70% argon, 30% oxygen, sputtering pressure...
・8 X 10-4Torr discharge voltage...400V/
1 Target discharge current: 3 A The color tone of the obtained thin film layer-forming fiber body was yellowish green.

Example 10 Using the polyester cloth foil used in Example 1, a multi-target type DC magnetron sputtering device (
(manufactured by Sanyo Shinku Kogyo Co., Ltd.), and a metal thin film layer and a metal oxide compound thin film layer were formed under the following conditions.

[Conditions for forming the first layer thin film layer]: Target: Indium tin (tin content: 5 mol%) Sputtering gas: Argon sputtering pressure: 8 x 10-'Torr discharge voltage: 400V/1 Target discharge current: 3 A Film thickness: 800 Å [Second layer = metal oxide compound thin film layer formation conditions]: Target: indium tin (tin content: 5 mol%) Sputtering gas: argon 70% Ten oxygen 30% sputtering pressure...8 x 10-'Torr discharge voltage...
400V/1 target discharge current: 3A Film thickness: 2000 Å The obtained indium tin oxide/indium tin thin film layer-formed fiber had a yellow color tone.

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between titanium oxide film thickness and hue in fibers obtained by the method of the present invention. 2 to 7 are graphs showing the optical characteristics of the fiber body according to the present invention, which is provided with a metal thin film layer serving as the first layer and a transparent metal compound thin film layer serving as the second layer. FIG. 8 is a graph showing the reflectance in the visible region of the fibrous body of the present invention, which includes an A1 metal thin film layer as the first layer and a transparent aluminum nitride thin film layer as the second layer. FIG. 9 is a graph showing the reflectance in the visible region of the fibrous body of the present invention comprising a metallic titanium thin film layer and a transparent 5i02 thin film layer. FIG. 10 is a graph showing the reflectance in the visible region of the fibrous body of the present invention comprising a metallic titanium thin film layer and a transparent MgF2 thin film layer. (Above) Figure 1 Shallow Length (nm) Figure 3 Reverse Length (nm) Figure 5 Tomonaga (nm) Figure 5 Wire Weight (nm) Figure 8 Temporary Length ( nm) 10th Figure 00 00 :, Mugi 00 Length (nm) 00

Claims (2)

[Claims] (1) A fibrous body having an interference color, characterized by comprising a metal thin film layer and a light-transmitting metal compound thin film layer in this order. (2) The fibrous body is maintained in a reduced pressure or vacuum state, and a metal thin film layer formation treatment is performed in the presence or absence of an inert gas, and then a metal compound thin film layer is formed in the presence of an inert gas containing a metal compound forming component. A method for producing a fibrous body having an interference color and comprising a metal thin film layer and a light-transmitting metal compound thin film layer, the method comprising performing a layer forming process.