JP2931437B2 - 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 scale structure of a morpho butterfly 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), it 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 a light reflecting layer, an interference resin layer or a transparent metal layer, and a translucent metal layer, and is a technique for enabling adhesive transfer by an adhesive layer. Further, as a method for 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 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. In contrast, the technology consisting of three or more thin films can provide a film or molded article of a reasonable level in 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 oxides, nitrides, carbides, and fluorides in sputtering is extremely slow, and the production cost is extremely high and the productivity is low in such a sputtered film formation method requiring a long time. It has little industrial meaning. Further, the two-layer sputtering method is not preferable because of the large change in the feeling such as the hardness of clothing and the like due to this treatment.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to produce a light interference coloring fiber sheet at a relatively low cost, and to increase the line speed to a level capable of industrial production. An object of the present invention is to provide a light interference coloring fiber sheet having little change in feel such as hardness.

[0008]

According to the present invention, there is provided a fiber sheet having a metal thin film layer having a thickness of 0.05 to 0.2 μm on at least one side thereof, and a refractive index of 1.35 to 0.2 μm on the metal thin film layer.
A fibrous sheet comprising an organic three-dimensional crosslinked thin film layer having a thickness of 3.5 and a thickness of 0.05 to 1 μm.

The present invention further comprises forming a metal thin film layer having a thickness of 0.05 to 0.2 μm on at least one surface of the fiber sheet,
A refractive index of 1.35 was formed on the thin film layer by a plasma polymerization method.
A method for producing a fiber sheet, comprising forming an organic thin film layer having a thickness of from 0.05 to 3.5 and a thickness of from 0.05 to 1 μm.

[0010] The fiber sheet referred to in the present invention means a woven fabric, a knitted fabric, a nonwoven fabric or the like, and may be colored with a dye or a pigment. Further, a resin or the like may be impregnated. Among the fibrous sheets, because they can exhibit the iridescent effect and interference color sufficiently, they are especially those with irregular cross-section fibers or those with so-called roughened fibers with fine irregularities formed on the fiber surface, and furthermore, anisotropic Fabrics (twill, satin, etc.) and knits are effective. In order to obtain a vivid beetle effect with the fiber sheet, it is preferable that the thickness of the film formed on the surface of the fiber sheet be more favorable in the direction. Preferably, a sheet is used. In the present invention, at least one side means one side or both sides, but usually only one side used on the front side is sufficient.

The first layer (thin metal layer) may be any film that effectively reflects visible light that has entered and passed through the second layer at the interface between the first and second layers. If the first layer is a colored thin film such as gold or copper, its color affects the interference color, and the saturation of the interference color tends to be low. Therefore, it is desirable that the reflectance for visible light is relatively flat. These metals include Ti, Al, C
r, Fe, Mo, Nb, W, Ni, Co, Ta, Zr,
V, Mn or a mixture thereof.
i, Cr, Al, and Fe are preferable in that they exhibit flat reflectance.

[0012] The thickness of these films is 0.05 μm to
It is desirable to be within the range of 0.2 μm. When the thickness is less than 0.05 μm, the effect as a reflection surface is small, the reflectance is small, the brightness of the interference color is low, and 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 3.5. 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 3.5, an interference color appears in a thin film, but a slight difference in the film thickness changes the interference color. And the production stability deteriorates. In particular, the refractive index of the organic thin film is most preferably in the range of 1.35 to 1.6.

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, the productivity will decrease, and the hardness of the fiber sheet will increase and the hand change will be large. In particular, the thickness is preferably in the range of 0.1 μm to 0.5 μm. 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, between the refractive index of the first layer (n ₁ = n ₁ −ik ₁ ) (complex refractive index) and the refractive index of the second layer (n ₂ ) and the film thickness (d ₂ ), It is desirable to have a combination that satisfies the expression.

[0015]

(Equation 1)

In addition, a thin film forming method using a plasma polymerization method is used from the viewpoint of uniformity of the thickness of the second layer, that is, vivid interference color development. 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 3.5 or less, especially 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. Fluorine-based compound as the example _{C 2 F 4, C 3 F} 6, C 3 F 6 O, there is an equal CF ₄ +
A mixed system of H ₂ , C ₃ F ₈ + H _{2 and the} like may be used. As the silane-based compound, a vinylsilane-based compound is preferable, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyldimethoxyethoxysilane.

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.

[0019]

【Example】

Examples 1-3 and Comparative Examples 1-3 Nylon 6 50 ^d / 20 _{f for} the warp and Nylon 6 for the weft
A 1/3 twill fabric using 75 ^d / 30 _f was desizing and scouring according to a conventional method, and set with a 170 ° C. hot air drier. This fabric was set in a sputtering apparatus having a high frequency power supply of 13.56 MHZ manufactured by Tokuda Seisakusho and evacuated to 10 ^-4 Torr. Ti was used as a target, an argon gas was flowed at a flow rate of 50 ^CC / min as a gas, the degree of vacuum in the system was controlled at 10 ⁻³ Torr, and Ti was sputtered for 5 minutes at an output of 100 W to form a 0.1 μm Ti thin film ( n ₁ ⁺
= 2.5-3.1 ia at 500 nm complex refractive index).

After the discharge is stopped, oxygen gas is ^supplied at 15 ^CC
/ Min, argon gas was flowed at 50 ^CC / min, the degree of vacuum in the system was controlled at 10 ^-3 Torr, and the film was formed for 30, 60, and 90 minutes, and the refractive index was 0.07, 0.15, and 0.21. 7
Was formed (Comparative Examples 1 and 2, respectively).
2, 3).

On the other hand, after forming a 0.1 μm Ti thin film, the sample was taken out and set in a plasma polymerization apparatus having a bell jar type 13.56 MHZ high frequency power supply.
After evacuation to 0 ^-2 Torr, C ₃ F ₆ O gas was flowed at 50 ^CC / min and the inside of the system was controlled to 0.1 Torr. Organic thin films having a layer refractive index of 1.38 and film thicknesses of 0.1 μ, 0.2 μ, and 0.3 μ were formed (Examples 1, 2, and 3). Example 1,
Nos. 2 and 3 exhibited interference colors of light blue, purple, and yellow-green, respectively, and the color changed depending on the viewing direction, and had a vivid iridescent effect. Further, there was little change in the feeling of the fabric after setting and the gloss was maintained.

On the other hand, Comparative Examples 1, 2, and 3 were also light blue,
It had purple and yellow-green interference colors and an iridescent effect. However, the one with a sputtering time of 30 minutes had insufficient interference color and an iridescent effect. Had decreased. In the case of the clothes of the examples, the clothes had warm features as compared with the comparative examples.

Examples 4 and 5 Polyethylene terephthalate containing 3 wt% of colloidal silica (average particle size of 30 μm) was colloidal with polyethylene terephthalate-based polyester obtained by copolymerizing 8 mol% of polymer A with [η] = 0.68 and isophthalic acid at 8 mol%. [Η] = 3 wt% containing silica (average particle size 30 μm) =
75 ^d arranged as in FIG. 1 from 0.76 polymer B
/ _24f composite drawn yarn was obtained. Five-weft satin was woven using a polyethylene terephthalate fiber having a round cross section (containing 3 wt% of colloidal silica having an average particle size of 30 μm) of 50 ^d / 36 _f for the warp and the above-mentioned composite stretched yarn for the weft. (C woven fabric).

On the other hand, as a comparison, a polyethylene terephthalate semi-dal yarn 50 ^d / 36 _f and a round cross-section drawn yarn 75 ^d / 36 _f
Using 24 _f for the warp and the weft, weft weft satin was woven. (D woven fabric). After scouring and presetting both of them according to a conventional method, the weight was reduced at a temperature of 4% NaOH at 95 ° C. for 40 minutes.

The fiber surface of the C woven fabric is formed into a roughened fiber with irregularities of 0.2 to 0.7 μm, and the weft develops a twist, as shown in FIG. 2 (cross section of the weft in the woven fabric). Had been arranged. On the other hand, the D woven fabric was not a roughened fiber to the extent that irregularities of 1 μ or more were scattered in some places.
On these fabrics, Cr was added to the first layer under the same conditions as in Example 3.
To form a 0.15 μm Cr thin film (n ₁ = 3.
28-1.38 iat (complex refractive index of 608 nm), and a 0.5 μm organic thin film having a refractive index of 1.47 was formed by vinyltrimethoxysilane instead of C ₃ F ₆ O.

In the case of Example 4 (woven fabric C) using the composite fiber of the roughened fiber, an extremely clear and bright pink interference color and a directional iridescent effect were obtained. On the other hand, in the case of the D woven fabric using semi-dal yarn (Example 5), a pink interference color and an iridescent effect were obtained, although slightly inferior to Example 4.
However, both the C woven fabric and the D woven fabric did not differ from the feeling after weight loss. The fabrics obtained in Examples 4 and 5 were washed in a washing machine for about 200 minutes and then air-dried. The woven fabric obtained in Example 5 was partially peeled off at the interface between the fiber surface and the first Cr layer to reduce interference colors, but the woven fabric obtained in Example 4 did not show any peeling and was washed. It had the same interference color and iridescence as before.

[0027]

The fiber sheet of the present invention has a so-called beetle effect in which the sheet is colored in different colors depending on the viewing angle, and the line speed is reduced to such a level that such a sheet can be produced relatively inexpensively and industrially. It can be manufactured by a manufacturing method that can be increased. Further, the fiber sheet of the present invention has little change in hand such as hardness.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a fiber suitably used for a fiber sheet of the present invention.

FIG. 2 is a cross-sectional view showing an arrangement of fibers when a woven fabric is prepared using the fibers of FIG.

[Explanation of symbols]

A Polyethylene terephthalate containing colloidal silica B Polyethylene terephthalate containing isophthalic acid containing colloidal silica

Continuation of the front page (58) Field surveyed (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 0.05 to 0.2 μm on at least one surface thereof, and a refractive index of 1.35 to 3.5 and a film thickness of 0.3 μm on the metal thin film layer. 05-1μ
m. A fiber sheet having an organic three-dimensionally crosslinked thin film layer. 2. A film having a thickness of at least one side of at least one side of a fiber sheet.
A metal thin film layer having a thickness of 0.05 to 0.2 μm is formed, and an organic thin film layer having a refractive index of 1.35 to 3.5 and a thickness of 0.05 to 1 μm is formed on the thin film layer by plasma polymerization. A method for producing a fiber sheet characterized by the above-mentioned.