JP2931459B2 - Fiber sheet and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber sheet for producing color interference light and a method for producing the same. The invention relates to a method for producing a color using a light interference phenomenon without using a coloring agent such as a dye or a pigment. The present invention relates to a fiber sheet having a so-called beetle effect, which is colored in different colors depending on a viewing angle when applied.

[0002]

2. Description of the Related Art Recently, a fiber whose color tone changes due to a change in temperature,
Various fiber products have been released, such as a fiber that changes color when irradiated with ultraviolet light, and a fiber that mimics the morphology of the morpho butterfly scale and produces a vivid color. However, these are due to coloring by dyes and pigments, and the color is such that the dyes and pigments are visible light (wavelength 35).
(0 to 800 nm), which is colored by partially absorbing light.

On the other hand, a transparent thin film such as a soap bubble or an oil film spread on the water surface causes a beautiful rainbow interference fringe due to sunlight. This rainbow color is caused by interference of light reflected from the thin film. If such an interference color can be reproduced on a sheet-like structure, a color tone completely different from that obtained by a conventional coloring method can be obtained.

[0004] As a method of expressing an interference color in a film or a molded product, a method using a transfer foil has conventionally been proposed.
There are methods described in JP-A-1-14055 and JP-B-3-2079. Each of these methods is an interference method including three layers of a light reflection layer, an interference resin layer or a transparent metal layer, and a translucent metal layer, and is a technique of enabling adhesive transfer by an adhesive layer. Further, as a method of giving an interference color to a sheet or a molded product, there is a method described in JP-B-51-33589 and JP-B-3-4040. These methods are interference systems including three layers of a light reflecting layer, an interference layer and a translucent layer, like the transfer foil.

As described in Japanese Patent Publication No. 51-33589, such a three-layer interference color imparting technique is disclosed in Japanese Patent Publication No. 37-8731 and a single-layer film described in Japanese Patent Publication No. 37-8731. The two-layer film described in JP-A-44-27173 has the disadvantage that the hue and saturation of the interference color are low, the adhesion to the base and the stability are poor, the mass production is difficult, and a satisfactory interference color cannot be obtained. On the other hand, a technique comprising three or more thin films can provide a film or molded article at a reasonable level with respect to the above points. However, even if a thin film technology having three or more layers is used, satisfactory results cannot be obtained when interference is imparted on the fiber sheet. Had the problem of becoming

[0006] From this viewpoint, recently, the processing technology Vol.
No. 25, No. 12 (1990) 761, on a fiber sheet, a titanium film having good adhesion to fibers and an appropriate reflectance is formed as a first layer, and a transparent thin film such as titanium oxide is formed as a second layer by sputtering. The disclosed fiber sheet that develops color by interference is disclosed. In this report,
It is described that nitride, carbide, fluoride, and the like are effective as the second layer in addition to oxide. However, in order to effectively use these films as interference colors, 0.05 to
A film thickness of 0.2 μm is required, and a sputtering time of at least one hour is required even with a high-performance sputtering machine. This is because the film formation rate of oxide, nitride, carbide, and fluoride in sputtering is extremely slow, and the production cost is extremely high and the productivity is low in such a sputtering film formation method that requires a long time. It has little industrial meaning. Further, the expression of the light interference color is also affected by the surface structure (woven or knitted structure, constituent yarns, etc.) of the fiber sheet, and it is extremely difficult to develop the interference color depending on the structure or the constituent yarn. For example, as a material that is unlikely to exhibit a clear interference color, there are cases where the yarn constituting the woven or knitted material is a false twisted yarn, a strongly twisted yarn, a roughened fiber, or the like.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to produce a clear light interference coloring fiber sheet at a relatively low cost, to increase the line speed to a level capable of industrial production, and to provide a two-layer thin film by sputtering. The present invention provides a light interference coloring fiber sheet having less change in hand feeling such as hardness than that of the above.

[0008]

According to the present invention, there is provided a fiber sheet having a metal thin film layer having a thickness of 0.02 to 0.2 μm on at least one surface thereof, and a refractive index of 1.35 to 2.0 μm on the metal thin film layer. 2.
A fiber sheet having an organic three-dimensional crosslinked thin film layer having a thickness of 0.05 to 1 μm and a reflectivity of 20 to 50% on its surface.

The present invention also relates to a step (A) of forming a metal thin film layer having a thickness of 0.02 to 0.2 μm on at least one side of the fiber sheet, and (B) a step of forming a metal thin film on the thin film layer by a plasma polymerization method. Thickness 0.05-1 μm with ratio 1.35-2.0
(A), (B), (C), and (C) a step of calendering the fiber sheet.
(A) (C) (B), (C) (A) (B) It is a manufacturing method of the fiber sheet characterized by performing in any order.

[0010] The fiber sheet referred to in the present invention means a woven fabric, a knitted fabric, a nonwoven fabric, a laminated fabric and the like, and may be colored with a dye or a pigment. Further, a resin such as a hydrophilic agent, a water repellent, and a finishing agent may be impregnated. Ancillary processing such as wrinkle processing may be performed. The cross-sectional shape of the yarn constituting the fiber sheet can be raw yarn or processed yarn (false twist, Indoro),
Any shape such as roughening may be used. There is no particular limitation on the woven structure, the knitted structure, or the like, and any structure may be used. In the present invention, at least one side means one side or both sides, but only one side usually used on the front side is sufficient.

The first layer (metal thin film layer) may be any film that effectively reflects visible light passing through the second layer at the interface between the first and second layers. When the first layer is a colored thin film such as gold or copper, a portion of a visible light having a certain wavelength is absorbed by the first layer, so that the color of the interference color is inferior. Therefore, it is desirable that the reflectance for visible light be relatively flat. These metals include Ti, Al, Cr, Fe, Mo, Nb,
W, Ni, Co, Ta, Zr, V, Mn or a mixture thereof, and particularly, Ti, Cr, Al, Fe,
Stainless steel and Hastelloy are preferable in that they exhibit flat reflectance.

[0012] The thickness of these films is 0.02 µm to
It is desirable to be within the range of 0.2 μm. When the thickness is less than 0.02 μm, the effect as a reflection surface is small, and the brightness of the interference color is reduced, so that only a dark interference color can be obtained. Conversely, if it exceeds 0.2 μm, the fiber sheet becomes hard, and the change in hand is large, which is not preferable. The first layer preferably has good adhesion to the fiber sheet, and from this viewpoint, the method for forming the first layer is preferably a vacuum deposition method or a sputtering method.

The second layer (organic thin film layer) is first required to have good adhesion to the first layer, is further transparent, and has a refractive index in the range of 1.35 to 2.0. It is required to be within. In the case of an organic thin film having a refractive index of less than 1.35, interference color does not appear unless the film thickness is considerably increased, resulting in low productivity. When the refractive index exceeds 2.0, an interference color appears in a thin film, but a slight difference in the film thickness changes the interference color. And production stability deteriorates. In particular, the refractive index of the organic thin film is 1.35 to 1.6.
Is most desirable.

The thickness of the second layer is preferably in the range of 0.05 to 1 μm. If it is less than 0.05 μm, a vivid interference color cannot be obtained, and if it exceeds 1 μm, it takes a long time to form a film, and the productivity decreases, and the hardness of the fiber sheet increases and the hand change is large. Particularly, the film thickness is 0.1 μm to 0.1 μm.
A range of 5 μm is preferred. When the film thickness is in this range, there is little change in feeling, etc., unlike a sputtered film such as the first layer. However, in principle, the refractive index of the first layer (n ₁ = n ₁ -ik
₁ ) (complex refractive index), the refractive index (n ₂ ) of the second layer, and the film thickness (d
_It is desirable to use a combination that satisfies the following equation with ₂ ).

[0015]

(Equation 1)

Further, a thin film forming method by a plasma polymerization method is used from the viewpoint of uniformity of the thickness of the second layer, that is, vivid interference color development without color unevenness. Plasma polymerization is a method of forming a three-dimensionally cross-linked thin film on an object by applying a high-frequency voltage between electrodes while supplying a polymerizable monomer under vacuum. It is most preferable in terms of film thickness controllability and pinhole free, and a film thickness uniformity that cannot be achieved by sputtering is obtained. Further, since the three-dimensional cross-linking is performed, sufficient film strength can be obtained in spite of being a thin film.

The refractive index is 1.35 or more and 2.0 or less, particularly 1.
As a monomer for forming a plasma polymerized film of 35 or more and 1.6 or less, a fluorine compound and a silane compound are preferable. From such a compound, a film having a uniform thickness can be formed by a plasma polymerization method, and a film having extremely excellent transparency can be formed. Examples of fluorine compounds include C ₂ F ₄ , C ₃ F ₆ , C ₃ F ₆ O, etc.
A mixed system of ₄ + H ₂ , C ₃ F ₆ + H ₂ or the like may be used. As the silane-based compound, a vinylsilane-based compound is preferable, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyldimethoxyethoxysilane. A silane compound is preferred from the viewpoint of the adhesive strength to the first layer.

Further, in the present invention, if necessary, other layers may be accumulated on the organic three-dimensionally crosslinked thin film layer as long as the light interference coloring property of the present invention is not significantly impaired. Finishing processing may be performed.

The reflectivity of the interference surface of the completed interference cloth is preferably 20 to 50% in view of color vividness. 2
If it is less than 0%, the interference color is dark, and if it exceeds 50%, the surface reflection is too strong to make the interference color difficult to see. In addition,
What is the reflectance in the light?
If the measurement wavelengths are the same, it means that they have the same reflectance.
To taste. As a method for controlling the reflectivity of the interference surface to 20 to 50%, calendar processing is most suitable. In the calendering process, the fiber sheet nips between the two heating rolls and runs to flatten the sheet surface.
The degree of planarization can be changed by changing the temperature and speed of the heating roll.

Particularly effective effects of calendering are woven and knitted fabrics using structurally processed yarns, woven and knitted fabrics using strongly twisted yarns, woven and knitted fabrics using roughened fibers, and woven fabrics using processed yarns (false twisted yarns and Indian low yarns). A sheet originally having little surface reflection such as a knitted fabric may be used.

In the method of the present invention, the step (A)
The order of the steps (B) and (C) is important, and as described above, (A), (B), (C), and (A)
(C), (B), (C), (A), and (B). By performing the processing in this order, it is possible to obtain an optical interference cloth having a target reflectance of 20 to 50%. The calendering is generally performed on the entire surface of the fiber sheet, but may be partially calendered (embossed or the like) depending on the purpose. In this case, for example, if a calender roll having a pattern of flowers, butterflies, etc. is used, a fiber sheet partially calendered is completed. When it is desired to impart water repellency or the like, before or after the step (A),
It can be processed without any problem even if applied after the step (B) and after the step (C), and the same performance can be obtained.

In the present invention, the reflectance is measured by the following method. That is, using a self-spectrophotometer U-3400 manufactured by Hitachi, Ltd., the visible light range (380
７780 nm). The reflectance of 20 to 50% referred to in the present invention refers to any wavelength within this visible light region .
Even if the measurement is performed, it means that the reflectance is always in the range of 20% or more and 50% or less. In addition, any of the interference coloring parts
At the same point, the same reflectance has the same wavelength at the same wavelength.

[0023]

The present invention will be described in detail with reference to the following examples. Example 1 and Comparative Example 1 Polyester 75 ^dr / 36f false twist yarn for warp and polyester 50 ^dr / 24f strong twist yarn (2000 T / M) for weft yarn
Sizing and refining the plain woven fabric using
Heat set for 1 minute. This fabric is manufactured by Tokuda Seisakusho 13.5
It was set in a sputtering apparatus having a 6 MHz high frequency power supply, and evacuated to 10 ^-4 Torr. Hastelloy was used as the target, and argon gas was used as the gas.
Flow at a flow rate of 0 cc / min and reduce the degree of vacuum in the system to 10 ^-3 Torr
, And Hastelloy was sputtered with an output of 100 W for 5 minutes to form a 0.1 μm Hastelloy thin film.

The woven fabric was taken out of the sputtering apparatus and set in a bell jar type plasma polymerization apparatus having a 13.56 MHz high frequency power supply, and was set at 10 ^-2 Torr.
After vacuum evacuation, C ₃ F ₆ gas is flowed at a flow rate of 30 cc / min.
Control the degree of vacuum in the system to 0.1 Torr and 50W
Plasma polymerization is performed for 2 minutes and 4 minutes with an output of 0.2 and a film thickness of 0.2
Organic thin films (refractive index: 1.38) of μm and 0.4 μm were formed. The fabric was taken out of the plasma polymerization apparatus, each sample was divided into halves, half of which was stopped processing at this point (Comparative Example 1), and the other half was used for calendering. The calendering is performed using a metal-metal roll type calendering apparatus, and the roll temperature is set to 130.
C., and the time during which the fabric contacted the metal roll was 1 second. (Example 1)

In Example 1, the organic thin film having a thickness of 0.2 μm has a bright pink iridescent interference color.
Those having a thickness of 4 μm had a bright green iridescent interference color. When the reflectance in the visible light region was measured by a spectrophotometer (Hitachi Ltd .: U-3400), the minimum values of the reflectance were 24% and 26% (450n , respectively).
m) , the highest values were 34% and 35% (550 nm) . On the other hand, the organic thin film without calendering of Comparative Example 1,
With a thickness of 0.2 μm, a dark pink interference color was observed, but the iridescent effect was hardly exhibited. In addition, thickness 0.
In the case of 4 μm, a dark green interference color can be seen,
The iridescent effect was hardly apparent. When the reflectance of the visible light region was measured by a spectrophotometer, respectively anti
The lowest value of Iritsu is 12%, 13% (450nm) , the highest value
Was 14% and 15% (550 nm) .

Example 2 and Comparative Example 2 A satin-textured woven fabric using an indolo yarn of polyester 75 ^dr / 24f for both the warp and the weft was subjected to desizing and refining according to a conventional method, and heat set at 170 ° C. for 1 minute. The woven fabric was rolled at a roll temperature of 160 using the same calender as in Example 1.
The film was calendered at a temperature of 1 ° C. and a contact time of 1 second with the roll. This calendar fabric is made by Tokuda Seisakusho 1
The apparatus was set in a sputtering apparatus having a high frequency power supply of 3.56 MHz and evacuated to 10 ^-4 Torr. Titanium as target and 5 argon gas as gas
Flow at a flow rate of 0 cc / min and reduce the degree of vacuum in the system to 10 ^-3 Torr.
r, and titanium was sputtered at an output of 100 W for 5 minutes to form a titanium thin film having a thickness of 0.1 μm. The woven fabric was taken out of the sputtering apparatus, set in a bell jar type plasma polymerization apparatus having a high frequency power supply of 110 KHz, evacuated to 10 ⁻² Torr, and then flowed C ₂ F ₄ gas at a flow rate of 30 cc / min.
Control the degree of vacuum in the system to 0.2 Torr, and
Plasma polymerization was performed for 2 minutes and 5 minutes at an output of W, and the film thickness was reduced to 0.
Organic thin films (refractive index: 1.38) of 2 μm and 0.5 μm were formed. Example 2 In Comparative Example 2, sputtering → plasma polymerization was performed under the same conditions as in Example 2 without performing the calendering step in the processing steps of Example 2. (Comparative Example 2)

The thickness of the organic thin film obtained in Example 2 was 0.2 μm.
m had a bright pink iridescent interference color, and 0.5 μm had a vivid yellow-green iridescent interference color. When the reflectance in the visible light region was measured with a spectrophotometer, the minimum value of the reflectance was 2
6%, 28% (500 nm) , the highest values are 39%, 40%
(600 nm) . In the case of the organic thin film having a thickness of 0.2 μm obtained in Comparative Example 2, the interference color was slightly visible. The one with a thickness of 0.5 μm showed a dark green color but was not an interference cloth. When the reflectance at these visible region was measured with a spectrophotometer, it
The lowest values of reflectivity are 9%, 8% (460nm) and the highest, respectively.
The values were 11% and 10% (540 nm) .

[0028] using a strong twisted yarn, splittable fibers 75 ^dr / 36f polyester / nylon weft 2000T / M of Example 3 and polyester 50 ^dr / 24f with the addition of silica having a particle size 45Emumyu 3% in Comparative Example 3 the warp A plain woven fabric was prepared by the above method, and then desizing and refining were performed according to a conventional method, followed by heat setting at 170 ° C for 1 minute. The woven fabric is subjected to a division treatment in a 70% bath of benzyl alcohol 10% / Sunmol BK 2% for 15 minutes.
Weight loss processing was performed in an OH 95 ° C bath for 40 minutes. As a result, this woven fabric is a roughened fiber whose warp has a weight loss rate of 20%,
The weft became 73 ^dr / 396f ultrafine fiber. The woven fabric was set in a sputtering apparatus having a 13.56 MHz high frequency power supply manufactured by Tokuda Seisakusho and evacuated to 10 ^-4 Torr. Using stainless steel as a target, flowing argon gas at a flow rate of 50 cc / min and controlling the degree of vacuum in the system to 10 ⁻³ Torr,
Sputter stainless steel for 5 minutes with the output of
A stainless thin film having a thickness of 0.1 μm was formed. The woven fabric was calendered using the same calender apparatus as in Example 1 under the conditions of a roll temperature of 160 ° C. and a contact time of 1 second with the roll. The calendered fabric was set in a bell jar type plasma polymerization apparatus having a high frequency power supply of 110 KHz, evacuated to 10 ^-2 Torr, and then flowed vinyl triethoxysilane monomer at a flow rate of 5 cc / min to reduce the degree of vacuum in the system to 0. At 0.3 Torr, plasma polymerization was performed for 2 minutes and 4 minutes at an output of 20 W to form an organic thin film (refractive index: 1.41) having a film thickness of 0.22 μm and 0.45 μm. (Example 3)

On the other hand, in Comparative Example 3, the calendering step in the processing steps of Example 3 was not performed, and the other steps were performed under the same conditions as in Example 3. (Comparative Example 3)

The thickness of the organic thin film obtained in Example 3 was 0.22.
The μm one had a bright pink iridescent interference color, and the 0.45 μm one had a vivid purple iridescent interference color. When the reflectance in the visible light region was measured by a spectrophotometer, the minimum value of the reflectance was 23
%, 22% (550 nm) , the highest values are 44%, 45%
(700 nm) . On the other hand, the organic thin film having a thickness of 0.22 μm obtained in Comparative Example 3 had a dark pink interference color and the 0.45 μm organic thin film had a dark blue-violet interference color. The products also did not seem to have commercial value as interference cloth. When the reflectance at these visible region was measured with a spectrophotometer, respectively reflectance
The minimum value is 10%, 10% (500 nm) , and the maximum value is 1
4% and 12% (680 nm) .

[0031]

Of course, in Examples 2 and 3, if the same calender roll as that of Example 4 is used, the same interference cloth as that of Example 4 can be obtained. By changing the pattern of the calendar roll, various things can be obtained.

[0033]

The present invention is characterized in that a vivid interference color can be imparted to a woven or knitted fabric having a small surface reflection, but a vivid interference color can be developed by using a calendering process, which has been conventionally difficult. It is.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-82881 (JP, A) JP-A-62-170510 (JP, A) JP-A-61-102300 (JP, A) 41927 (JP, U) JP44-27173 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) D06M 11/00-11/84 D06M 15/00-15/715 D06Q 1/00-1/14

Claims (2)

(57) [Claims] 1. A fiber sheet having a metal thin film layer having a thickness of 0.02 to 0.2 μm on at least one surface thereof, and a refractive index of 1.35 to 2.0 and a film thickness of 0.3 to 0.2 μm on the metal thin film layer. 05-1μ
A fiber sheet having an organic three-dimensionally crosslinked thin film layer having a reflectance of 20 to 50%. 2. A step of (A) forming a metal thin film layer having a thickness of 0.02 to 0.2 μm on at least one surface of the fiber sheet, and (B) a refractive index of 1.about. (A) (B) (C), (A) (C) the step of forming an organic thin film layer having a thickness of 0.05 to 1 μm with a thickness of 35 to 2.0 and the step of (C) calendering a fiber sheet.
(B), (C), (A) and (B) are performed in any order, The manufacturing method of the fiber sheet characterized by the above-mentioned.