JPH05156575A - Fibrous sheet and its production - Google Patents

Abstract

PURPOSE:To obtain a fibrous sheet having clear, iridescent interference color by forming a thin metallic film layer on a fibrous sheet followed by plasma polymerization to form thereon a thin organic film layer of specified refractive index followed by calendering. CONSTITUTION:A thin metallic film layer 0.02-0.2mum thick is formed on one side of a fibrous sheet by spattering technique, and a thin organic film layer 1.35-2.0 in refractive index (pref. fluorine-or silane-based compound) is then formed thereon by plasma polymerization process. Prior to or after the spattering or plasma polymerization, the fibrous sheet is calendered to smooth its surface, thus obtaining the objective fibrous sheet giving clear, iridescent interference color, thereby having iridescent effect. The metal to be used the thin metallic film layer is pref. Ti, Cr, or Fe.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light interference color-forming fiber sheet and a method for producing the same, which is used to fabricate a cloth or the like without using a coloring agent such as a dye or a pigment to develop a color by utilizing the light interference phenomenon. The present invention relates to a fiber sheet having a so-called iridescent effect that develops different colors depending on the viewing angle when applied.

[0002]

2. Description of the Related Art Recently, fibers whose color tone changes with changes in temperature,
Various fiber products have been put on the market, such as fibers whose color tone is changed by irradiation of ultraviolet rays, and fibers which imitate the scale structure of morpho butterflies and produce clear colors. However, these are due to the coloring by the dyes and pigments, and the color is the visible light (wavelength 35
Part of the light of 0 to 800 nm) is absorbed to make it appear colored.

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

As a method for developing an interference color in a film or a molded product, conventionally, a method using transfer foil has been used.
There are methods described in Japanese Patent Publication No. 1-14055 and Japanese Patent Publication No. 3-2079. Each of these methods is an interference method including three layers of a light ray reflection layer, an interference resin layer or a transparent metal layer, and a semitransparent metal layer, and is a technique that enables adhesive transfer by an adhesive layer. Further, as a method of imparting an interference color to a sheet or a molded article, there are methods described in Japanese Patent Publication No. 51-33589 and Japanese Patent Publication No. 3-4040. Similar to the transfer foil, these methods are an interference method including three layers of a light reflecting layer, an interference layer and a semitransparent layer.

As described in Japanese Patent Publication No. 51-33589, the single-layer film and the actual Japanese public disclosure disclosed in Japanese Patent Publication No. 37-8731 are disclosed in Japanese Patent Publication No. 51-33589. In the two-layer film described in Japanese Patent Laid-Open No. 44-27173, the hue and saturation of the interference color are low, and the adhesion and stability with the base are poor, mass production is difficult, and a satisfactory interference color cannot be obtained. In contrast to the above, the technique consisting of three or more layers of thin film can obtain a film or a molded product at a reasonable level with respect to the above points. However, even if a thin film technology with three or more layers is used, satisfactory results cannot be obtained when interference is provided on the fiber sheet, and it takes too much time and labor to form three or more layers, resulting in high cost. Had the problem of becoming.

From this point of view, recently, processing technology Vol.
No. 25, No. 12 (1990) 761, a titanium film having good adhesion to fibers and having a proper reflectance as a first layer and a transparent thin film such as titanium oxide as a second layer are formed on a fiber sheet by sputtering. Disclosed is a fiber sheet that develops color due to interference. In this report,
It is stated that, in addition to oxides, nitrides, carbides, fluorides, etc. are effective for the second layer. However, in order to effectively use these films as interference colors,
A film thickness of 0.2μ is required, and a sputtering time of at least 1 hour or more 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. Thus, in the sputtering film forming method that requires a long time, the manufacturing cost is extremely high and the productivity is low. It can be said that it has almost no industrial meaning. Furthermore, the expression of the light interference color is also influenced by the surface structure of the fiber sheet (woven or knitted structure, constituent yarn, etc.), and it is extremely difficult to develop the interference color depending on the structure or constituent yarn. For example, as a material that does not easily develop a clear interference color, there are cases where the yarn constituting the woven or knitted fabric is a false twisted yarn, a strongly twisted yarn, a roughened fiber, or the like.

[0007]

An object of the present invention is to produce a clear optical interference coloring fiber sheet at a relatively low cost and to increase the line speed to a level at which industrial production is possible. Further, a two-layer thin film formed by sputtering. The present invention provides an optical interference coloring fiber sheet with less change in hardness and other textures than the above.

[0008]

The present invention has a metal thin film layer having a film thickness of 0.02 to 0.2 μm on at least one side of a fiber sheet, and a refractive index of 1.35 to 35 on the metal thin film layer. 2.
A fiber sheet having an organic three-dimensional crosslinked thin film layer having a thickness of 0 to 0 and a film thickness of 0.05 to 1 μm, and having a reflectance of 20 to 50% on its surface.

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

The fiber sheet referred to in the present invention means a woven fabric, a knitted fabric, a non-woven fabric, a laminated fabric or the like, which may be colored with a dye or a pigment. In addition, a resin such as a hydrophilizing agent, a water repellent, and a finishing agent may be impregnated. Further, auxiliary processing such as wrinkling processing may be applied. The cross-sectional shape of the yarns that make up the fiber sheet can be raw yarn or processed yarn (false twist, indrow),
Any shape such as roughening may be used. Further, there is no particular preference for the woven structure, the knitted structure, etc., and any structure may be used. In the present invention, at least one side means one side or both sides, but one side usually used on the front side is sufficient.

The first layer (metal thin film layer) may be a film that effectively reflects visible light that has passed through the second layer at the interface between the first layer and the second layer. When the first layer is a colored thin film such as gold or copper, a portion of visible light having a certain wavelength is absorbed by the first layer, so that 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,
Examples thereof include W, Ni, Co, Ta, Zr, V, Mn, and mixtures thereof. Particularly, Ti, Cr, Al, Fe,
Stainless steel and Hastelloy are preferable in that they show a flat reflectance.

The film thickness of these is from 0.02 μm to
The range of 0.2 μm is desirable. When it is less than 0.02 μm, the effect as a reflecting surface is small, the brightness of the interference color is low, and only dark interference color is obtained. On the other hand, when it exceeds 0.2 μm, the fiber sheet becomes hard and the change in feeling is large, which is not preferable. The first layer preferably has good adhesiveness to the fiber sheet, and from this viewpoint, a vacuum vapor deposition method or a sputtering method is preferable as a method for forming the first layer.

The second layer (organic thin film layer) is first required to have good adhesiveness to the first layer, is further transparent, and has a refractive index in the range of 1.35 to 2.0. Required to be within. With an organic thin film having a refractive index of less than 1.35, interference colors do not appear unless the film thickness is made considerably thick, and the productivity is low. When the refractive index exceeds 2.0, interference color appears in a thin film, but since a slight difference in film thickness changes the interference color, uniform film thickness is required and high-level film thickness control is required. As a result, the production stability becomes poor. In particular, the organic thin film has a refractive index of 1.35 to 1.6.
The range of 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 bright interference color cannot be obtained, and if it exceeds 1 μm, it takes time to form a film, productivity is lowered, and the hardness of the fiber sheet is increased, resulting in a large change in feeling. In particular, the film thickness is 0.1 μm to 0.
The range of 5 μm is preferable. When the film thickness is in this range, unlike the sputtered film such as the first layer, the change in feeling and the like is small. However, in principle, the refractive index of the first layer (n ₁ = n ₁ −ik
₁ ) (complex refractive index), refractive index (n ₂ ) of second layer, film thickness (d
_It is desirable to have a combination that satisfies the following formula with ₂ ).

[0015]

[Equation 1]

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

Refractive index 1.35 to 2.0, especially 1.
A fluorine compound and a silane compound are preferable as the monomer for forming the plasma polymerized film of 35 or more and 1.6 or less. A film having a uniform film thickness can be formed from such a compound by a plasma polymerization method, and a film excellent in transparency can be formed. Examples of the fluorine-based compound include C ₂ F ₄ , C ₃ F ₆ , C ₃ F ₆ O, etc., and CF
A mixed system of ₄ + H ₂ , C ₃ F ₆ + H _2, etc. may be used. The silane-based compound is preferably a vinylsilane-based compound, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyldimethoxyethoxysilane. A silane compound is preferable from the viewpoint of the adhesive strength with the first layer.

Further, in the present invention, other layers may be accumulated on the organic three-dimensional crosslinked thin film layer, if necessary, within a range that does not significantly impair the light interference coloring property of the present invention. Finishing treatment may be performed.

Further, the reflectance of the interference surface of the finished interference cloth is preferably 20 to 50% in view of color vividness. Two
If it is less than 0%, the interference color is dark, and if it exceeds 50%, the surface reflection is too strong and the interference color becomes difficult to see. As a method of controlling the reflectance of the interference surface to 20 to 50%,
Calendering is optimal. In calendering, a fibrous sheet is nipped and runs between two heating rolls to flatten the sheet surface, and the degree of flattening can be changed by changing the temperature and speed of the heating rolls. ..

Particularly effective in calendering are woven and knitted fabrics that use structurally processed yarns, woven and knitted fabrics that use strongly twisted yarns, woven and knitted fabrics that use roughened fibers, and woven fabrics that use textured yarns (false twisting yarns, indrow yarns). A sheet such as a knitted fabric, which originally has a small surface reflection, can be mentioned.

In the method of the present invention, the step (A) above,
The order of the steps (B) and (C) is important, and as described above, (A), (B), (C), and (A)
The steps (C), (B), (C), (A), and (B) are performed in this order. By performing in this order, it is possible to obtain the optical interference cloth having the 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, a calender roll having a pattern such as flower buds and butterflies is used to form a partially calendered fiber sheet. If you want to impart water repellency, etc., before and after the step (A),
It can be processed without any problem even if it is applied after the step (B) or 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 Hitachi spectrophotometer U-3400 manufactured by Hitachi, Ltd.
The reflectance at 780 nm) is obtained. The reflectance of 20 to 50% in the present invention means that the reflectance is always in the range of 20% or more and 50% or less in this visible light region. Of course, when a calendar roll having a pattern is used, it means the reflectance of the surface-smoothed portion in order to give an interference color.

[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 for weft (2000 T / M)
The plain weaving fabric using is refined by desizing according to the usual method, and 170 ℃
Heat set for 1 minute. This woven fabric is manufactured by Tokuda Manufacturing Co., Ltd. 13.5
It was set in a sputtering apparatus having a high frequency power source of 6 MHz and evacuated to 10 ⁻⁴ Torr. Hastelloy was used as the target and argon gas was used as the gas.
The degree of vacuum in the flow system at a flow rate of 0 cc / min is set to 10 ⁻³ Torr.
Control was performed, and Hastelloy was sputtered for 5 minutes at an output of 100 W to form a Hastelloy thin film of 0.1 μm.

This woven fabric was taken out from the sputtering device and set in a bell jar type plasma polymerization device having a high frequency power source of 13.56 MHz, and was placed at 10 ^-2 Torr.
After evacuation, C ₃ F ₆ gas is flowed at a flow rate of 30 cc / min,
50W by controlling the vacuum degree in the system to 0.1 Torr
Plasma polymerization for 2 minutes and 4 minutes with the output of 0.2
An organic thin film (refractive index 1.38) having a thickness of 0.4 μm was formed. The woven fabric was taken out of the plasma polymerization apparatus, and each sample was divided into halves, half of which stopped processing at this point (Comparative Example 1), and the other half was used for calendering. For the calendering, a metal-metal roll type calender device is used, and the roll temperature is set to 130.
It was carried out under conditions that the fabric was in contact with the metal roll at 1 ° C. for 1 second. (Example 1)

In Example 1, the organic thin film having a thickness of 0.2 μm had a bright pink iridescent interference color,
Those of 4 μm had a bright green iridescent interference color. When the reflectance in these visible light regions was measured with a spectrophotometer (Hitachi: U-3400), the lowest part was 24%, 26%, and the highest part was 34%, 35%.
Met. On the other hand, the calendered organic thin film of Comparative Example 1 having a thickness of 0.2 μm showed a dark pink interference color but almost no iridescent effect. In the case of a thickness of 0.4 μm, a dark greenish interference color can be seen, but the iridescent effect was hardly exhibited. When the reflectance in these visible light regions is measured with a spectrophotometer, the lowest part is 12% and 13%, and the highest part is 14% and 15%, respectively.
Met.

Example 2 and Comparative Example 2 A woven fabric having a satin structure in which indolo yarn of polyester 75 ^dr / 24f was used for both warp and weft was desizing and refined according to a conventional method, and heat set at 170 ° C. for 1 minute. Using the same calendering device as in Example 1, this fabric was rolled at a roll temperature of 160.
Calendering was carried out under the condition that the temperature was in contact with the roll for 1 second. This calendar fabric is manufactured by Tokuda Manufacturing Co., Ltd. 1
It was set in a sputtering device having a high-frequency power supply of 3.56 MHz and evacuated to 10 ⁻⁴ Torr. Titanium is used as a target and argon gas is used as a gas.
Flow at a flow rate of 0 cc / min and set the degree of vacuum in the system to 10 ⁻³ Tor.
The titanium was sputtered for 5 minutes under the control of r at an output of 100 W to form a titanium thin film having a thickness of 0.1 μm. The woven fabric was taken out from the sputtering device, set in a bell jar type plasma polymerization device having a high frequency power source of 110 KHz, evacuated to 10 ^-2 Torr, and then C ₂ F ₄ gas was flowed at a flow rate of 30 cc / min.
The vacuum degree in the system is controlled to 0.2 Torr, 50
Plasma polymerization was performed for 2 minutes and 5 minutes at an output of W to obtain a film thickness of 0.
An organic thin film (refractive index 1.38) of 2 μm and 0.5 μm was 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 organic thin film obtained in Example 2 has a thickness of 0.2 μm.
The sample of m had a bright pink iridescent interference color, and the film of 0.5 μm had a bright yellow-green iridescent interference color. When the reflectance in these visible light regions is measured with a spectrophotometer, the lowest part is 26% and 2%, respectively.
8%, the highest part was 39%, 40%. In the organic thin film having a thickness of 0.2 μm obtained in Comparative Example 2, the interference color was slightly visible. In the case of 0.5 μm, a dark green color was observed, but it could not be said to be an interference cloth.
When the reflectance in these visible light regions was measured with a spectrophotometer, the lowest part was 9%, 8%, and the highest part was 11%, 10%.

Example 3 and Comparative Example 3 A 2000 T / M strongly twisted yarn of polyester 50 ^dr / 24f in which 3% of silica having a particle diameter of 45 mμ is added to a warp, and a polyester / nylon split type fiber 75 ^dr / 36f is used as a weft. A plain woven fabric was produced by the above method, further desizing and refining were carried out according to a conventional method, and heat set at 170 ° C. for 1 minute. This woven fabric is subjected to a split treatment for 15 minutes in a 70% bath of 10% benzyl alcohol / 2% Sanmor BK, washed with water, and then washed with 40 g / l Na.
Weight reduction processing was performed in an OH 95 ° C. bath for 40 minutes. As a result, in this woven fabric, the warp is a roughened fiber with a weight loss rate of 20%,
The weft became a composition of ultrafine fibers of 73 ^dr / 396f. This woven fabric was set in a sputtering device having a 13.56 MHz high frequency power source manufactured by Tokuda Seisakusho, and was evacuated to 10 ^-4 Torr. Using stainless steel as a target, argon gas as a gas was caused to flow at a flow rate of 50 cc / min to control the degree of vacuum in the system at 10 ⁻³ Torr, and 100 W
With the output of, stainless steel is sputtered for 5 minutes,
A stainless thin film having a thickness of 0.1 μm was formed. This woven fabric was calendered using the same blender device as in Example 1 under the conditions of a roll temperature of 160 ° C. and a time of contacting with the roll of 1 second. The calendered fabric was set in a bell jar type plasma polymerization apparatus having a high frequency power source of 110 KHz, and after vacuum evacuation to 10 ^-2 Torr, vinyltriethoxysilane monomer was flowed at a flow rate of 5 cc / min to reduce the degree of vacuum in the system to 0. It was controlled to 0.3 Torr, and plasma polymerization was performed at an output of 20 W for 2 minutes and 4 minutes 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 working steps of Example 3 was not performed, and the other steps were performed under the same conditions as in Example 3. (Comparative example 3)

Organic thin film thickness of 0.22 obtained in Example 3
The μm particles had a bright pink iridescent interference color, and the 0.45 μm particles had a bright purple iridescent interference color. When the reflectance in these visible light regions was measured with a spectrophotometer, the lowest part was 23% and 22%, respectively.
%, And the highest part was 44% and 45%. On the other hand, Comparative Example 3
The organic thin film having a thickness of 0.22 μm obtained in 1. had a dark pink interference color, and the organic thin film having a thickness of 0.45 μm had a dark blue-violet interference color. I didn't think it was worth the product. When the reflectance in these visible light regions was measured with a spectrophotometer, the lowest part was 10% and 10%, and the highest part was 14% and 12%.

Example 4 The same fabric as in Example 1 was subjected to the same processing. Calendering was performed by using two types of dark interference cloth of plasma polymerization upstream (0.2 μm, 0.4 μm) with calender rolls having rugged pattern of polka dots (convex pattern). The calender conditions were a roll temperature of 160 ° C., and the time for the fabric to contact the metal roll was 2 seconds. The reflectance of the polka dots is
In case of 0.2 μm, the lowest part is 25% and the highest part is 34%.
In the case of 0.4 μm, the lowest part was 27% and the highest part was 35%. The 0.2 μm-thick film was based on a dark pink interference color, and a very beautiful interference color of a bright blue partly polka dot pattern appeared. Similarly, with a thickness of 0.4 μ, an interference cloth having a dark green base color and a bright pink polka dot pattern was formed.

Of course, in the second and third embodiments, the same interference cloth as in the fourth embodiment can be obtained by using the canlender roll having the same specifications as in the fourth embodiment. In addition, various patterns can be obtained by changing the pattern of the calendar roll.

[0033]

INDUSTRIAL APPLICABILITY The present invention is characterized in that it is possible to give a vivid interference color to a woven or knitted fabric having a small amount of surface reflection, by using a calendar process, which is difficult to give a bright interference color. Is.

Claims (2)

[Claims] 1. A fiber sheet having a metal thin film layer having a film thickness of 0.02 to 0.2 μm on at least one surface thereof, and having a refractive index of 1.35 to 2.0 and a film thickness of 0. 05-1μ
A fiber sheet having an organic three-dimensional crosslinked thin film layer of m and having a reflectance of 20 to 50% on its surface. 2. A step of (A) forming a metal thin film layer having a film thickness of 0.02 to 0.2 μm on at least one side of a fiber sheet, (B) a refractive index of 1. by a plasma polymerization method on the thin film layer. (A), (B), (C), (A), (C), a step of forming an organic thin film layer having a thickness of 0.05 to 1 μm at 35 to 2.0, and a step of calendering a fiber sheet (C).
A method for producing a fiber sheet, which is carried out in any order of (B), (C), (A) and (B).