JP3242719B2 - Fiber sheet - 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 having a first colored portion exhibiting a vivid interference color due to interference of light and a second colored portion having a reflectance different from that of the first colored portion. Regarding the sheet.

[0002]

2. Description of the Related Art There have been proposed various techniques for obtaining interference colors. For example, as a means for imparting an interference color to a film or a molded product, Japanese Patent Publication No. 51-14055
JP, JP-B-51-33589, JP-B-3-2
No. 079, Japanese Patent Publication No. 3-4040, etc., all of which include three layers of a light reflecting layer, an interference layer, and a translucent (transparent) layer. Although molded articles can be provided with a certain level of interference color, their application to fiber sheets has not been perfected. Further, in the case of the three-layer formation, it takes too much time and labor, resulting in poor productivity.

Recently, processing technology Vol25, N
O. 12 (1990) 761 describes a technique for giving an interference color to a fiber sheet. In this method, the interference color is developed by forming a titanium thin film having good adhesiveness to the fiber and having an appropriate reflectance on the first layer and a transparent thin film such as titanium oxide on the second layer by sputtering. .
However, in this method, even if a high-performance magnetron sputtering apparatus is used, a sputtering time of one hour or more is required to form a thin film of the second layer, and from the viewpoint of manufacturing cost and low productivity, this method is industrially required. It must be said that practical application is extremely difficult.

The present inventors have previously described Japanese Patent Application Laid-Open No. 4-31667.
In JP-A-7, a three-dimensionally crosslinked organic thin film layer having a specific refractive index and film thickness is formed by a plasma polymerization method on a metal thin film layer and the thin film layer, so that an interference color-forming fiber sheet due to light can be formed in a short time. The invention has been proposed which can be manufactured with the above method, that is, which is advantageous for industrial use.

[0005] By the way, the inventors of the present invention have found that, in order to obtain a clear interference color, not only the materials or thicknesses of the thin films of the first layer and the second layer but also a woven or knitted fabric are required. It has been found that the yarn specifications (drawn yarn, false twisted yarn, twisted yarn, etc.) and the surface structure such as the weaving and knitting structure are also greatly related. That is,
In order to obtain a clear interference color, the fiber sheet surface must have an appropriate reflectance, and the yarn specifications can be used to reduce the reflection of light. It has been found that, when made, depending on the degree of reflectivity, not only a clear interference color is not obtained but also an interference color.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to produce a clear light interference coloring fiber sheet at a low cost, and to increase the line speed to a level at which industrial production is possible.
It is another object of the present invention to provide a light interference coloring fiber sheet having less change in feel such as hardness than a two-layer thin film formed by sputtering. In addition, the present invention combines not only color formation due to light interference but also color formation different in color tone from the light interference coloration, so that not only the light interference portion is clear but also other color and pattern portions stand out. It is intended to provide a colorful fiber sheet.

[0007]

Means for Solving the Problems According to the present invention, at least one side of the base fiber sheet has a thickness of 0.02 to 0.2 μm.
And a refractive index of 1.35 outside the metal thin film layer.
And an organic three-dimensional crosslinked thin film layer having a thickness of 0.05 to 1 μm and a calendering process in which the light reflectance in the visible light region falls within the range of 20 to 50%. > A fiber sheet characterized by having at least a first coloring portion and a second coloring portion having a reflectance different from that of the first coloring portion.

In the present invention, the term “base fiber sheet” (hereinafter referred to as “fiber sheet”) is used.
Simply referred to as a substrate) is a polyester,
It is made of synthetic fiber such as nylon (including a copolymer), and its form refers to a woven fabric, a knitted fabric, a nonwoven fabric, a laminate fabric, a coated fabric, or the like. These may be colored with dyes or pigments, but dark colors such as black and dark blue are not preferred in view of the vividness of the color of the resulting fiber sheet. Further, an additive effective for reducing the alkali content may be contained, and a resin such as a hydrophilizing agent, a water repellent, a finishing agent and the like may be attached. Further, additional processing such as wrinkles may be performed.

The cross-sectional shape of the yarn constituting the base material may be a round cross section, a modified cross section, or a mixed weave type of a modified cross section and a round cross section.
Further, they may have been subjected to a pretreatment such as surface roughening, false twisting, indole, air processing and the like. The weaving structure, the knitting structure and the like are not limited at all.

In the present invention, “at least one side”
Means one side or both sides, but usually only one side used on the front side of the cloth is sufficient. In the present invention, at least one surface has a first coloring portion and a second coloring portion described below.
And at least a color-developing portion.

The metal thin film layer, which is the first layer constituting the first color forming portion, effectively transmits visible light passing through the organic three-dimensional thin film layer, which is the second layer, at the interface between the first layer and the second layer. Any film that reflects light may be used. However, if the first layer is a colored thin film such as gold or copper, a part of a wavelength of visible light is absorbed by the first layer, and the color of the interference color becomes turbid. Therefore, it is desirable that the first layer has a relatively flat reflectance in the visible light region. Such metals include Ti, Al, Cr, Fe, Mo, N
b, 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.

These film thicknesses are 0.02 to 0.2 μm.
The range of m is preferred. When the thickness is less than 0.02 μm, the role as a reflection layer is small, the reflectance is low, and the brightness of the interference color is poor and only a dark interference color can be obtained. Conversely 0.2
If it exceeds μm, the fiber sheet becomes too hard and the change in hand is too large. There is also a disadvantage that it takes too much time to form a film. Particularly preferred is 0.03 μm to 0.1 μm.

The means for forming the first layer is preferably a vacuum deposition or sputtering method in consideration of the adhesion to the substrate.

The organic three-dimensional crosslinked thin film as the second layer formed outside the metal thin film layer as the first layer is required to have good adhesion to the first layer, and is further required to be transparent;
And it is required that the refractive index is in the range of 1.35 to 2.00. 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 2.00, an interference color appears at a thin film thickness, but a slight difference in the film thickness changes the interference color. It is required and production stability is deteriorated. A particularly preferable refractive index of the organic thin film is 1.35 to 1.6.
Range.

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 clear interference color cannot be obtained, and if it exceeds 1 μm, it takes a long time to form a film, resulting in low productivity and a hard fiber sheet. As a result, the optimum film thickness is 0.1 to
The range is 0.5 μm.

As the method of forming the organic three-dimensional crosslinked thin film as the second layer, a thin film formation method by plasma polymerization is preferably used from the viewpoint of uniformity of the film thickness, that is, a vivid interference color without color unevenness. .

In the plasma polymerization, a high-frequency voltage is applied between electrodes while supplying a polymerizable monomer under vacuum, thereby forming a three-dimensionally cross-linked thin film on the surface of the object to be processed. The organic three-dimensional crosslinked thin film formed by the plasma polymerization method is considerably superior to the sputtering method in terms of uniformity of the film thickness, controllability of the film thickness, pinholes, and the like. Further, since the three-dimensional cross-linking is performed, sufficient film strength can be obtained even though the film is thin.

As monomers for forming a plasma polymerized film having a refractive index of 1.35 or more and 2.0 or less, particularly 1.35 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 particularly by a plasma polymerization method, and a film having extremely excellent transparency can be formed.

Examples of the fluorine compound include C ₂ F ₄ ,
C ₃ F ₆ , C ₃ F ₆ O and the like, C ₂ F ₄ + H ₂ , C ₃ F ₆ + H ₂
And the like. In addition, as the silane compound,
Vinyl silane compounds are preferable, and examples thereof include vinyl trimethoxy silane, vinyl triethoxy silane, and vinyl dimethoxy ethoxy silane. From the standpoint of adhesive strength with the first layer, silane compounds are more preferred.

Further, in the present invention, if necessary, another layer may be laminated outside the organic three-dimensionally crosslinked thin film layer as long as the light interference coloring property of the present invention is not impaired. In the fiber sheet of the present invention, the base material may be partially dyed, but since the metal thin film layer as the first layer is usually formed on the entire surface of the base material, the base material is dyed in advance. It is not necessary to use a non-stained base material. However, if it is inconvenient to leave the back surface of the base material unstained, a pre-stained base material may be used.

The fibrous sheet surface on which the first and second thin film layers are formed on the surface of the substrate, that is, the surface that becomes the first color-developing portion, is a completed surface in the visible light region 380.
It is important that the reflectance of light of any wavelength falling within the wavelength region of ７780 nm falls within the range of 20 to 50%. If the light reflectance is out of this range, the brightness and clarity of the light interference color by the first layer and the second layer are lacking. That is, if the reflectance is less than 20%, light interference in this portion becomes a dark interference color, and if it exceeds 50%, the surface reflection becomes too strong and the interference color becomes difficult to see. In the present invention, the base material before forming the two thin film layers has the light reflectance in advance, or the base material that does not have the light reflectivity is previously processed before the formation of the two thin film layers by processing. Alternatively, the fiber sheet after the formation of the two thin film layers or the fiber sheet in the middle of the formation of the two thin film layers may have the light reflectance by processing.

The reflectance of the first colored portion is 20 to 50.
The most suitable way to control the percentage is calendering. The target reflectance can be obtained by controlling the temperature, pressure, and residence time of the calendar roll. Particularly effective effects (reflectance) of calendering are woven and knitted fabrics using structurally processed yarns, false twisted yarns, and indone yarns with swelling, and weaving using roughened fibers, strong twisted yarns, etc. It is a knit. These are usually 1
It has a light reflectance of about 0%, and the reflectance is increased by the calendering process.

The second colored portion of the fiber sheet is a portion having a different light reflectance in the visible light region from the first colored portion. The second coloring portion is roughly classified into two modes. First, there is a case where interference coloring by light is exhibited. In this case, the reflectivity of light may be in the range of 20 to 50%, but the reflectivity of the first and second colored portions is measured at a certain wavelength in the visible light region, for example, 500 nm. When compared, the reflectances of the two color portions are different, and if the difference is 3% or more, the color tone difference between the two color portions becomes clear. The second is a case where no interference coloring due to light is exhibited. In this case, when the light reflectance at the second colored portion is a color (black) portion close to 0%, when the light reflectance is a color (white) portion close to 100%, or when the light reflection is Even when the ratio is in the range of 20 to 50%, no interference coloring occurs, such as when the light reflectance does not exhibit interference coloring due to light over the range of 0 to 100%. In this case, the first coloring portion When the difference in gloss, especially the difference in reflectance, from the second colored portion is large, the color tone looks different. Specifically, it may be a colored portion of a print or the like placed on the outermost surface, or may be a colored portion in which the thin film layer is removed by some means to make the color of the original base material visible. The colored portion and the second colored portion are unique fabrics in which an interference light coloring portion and a non-interfering coloring portion are mixed.

The method for producing the fiber sheet of the present invention in the case where the second color forming portion is a print layer will be described. (A) Calendering step (light reflectance is set to 20 to 50%. Not necessary for certain woven or knitted fabrics),
(B) a first layer, a metal thin film forming step (sputtering), (C) a second layer, an organic three-dimensional crosslinked thin film forming step (plasma polymerization), and (D) a colored layer forming step (print etc.) It can also be obtained by using any of the steps described above in combination. (1): (A) → (B) → (C) → (D) (2): (A) → (B) → (D) → (C) (3): (B) → (A) → (C) → (D) (4): (B) → (A) → (D) → (C) (5): (B) → (D) → (C) → (A) (6) :( B) → (D) → (A) → (C)

The printing method may be either dye printing or pigment printing, but pigment printing is more preferable in order to obtain a clear color. In the case of dye printing, the dye penetrates into the organic thin film layer, and since the film thickness is small, the amount of exhaustion is limited. Therefore, the amount of dye for sufficient color development is insufficient, and the dye is not dyed into a clear color. However, if the dye is a dark color such as black, a certain degree of color development can be secured. In this regard,
In the case of pigment printing, a method in which a coloring agent is placed on a material to be dyed, and sufficient coloring can be achieved irrespective of a light color or a dark color. In order to further increase the adhesiveness between the pigment and the substrate, it is preferable to impart a hydrophilic group to the sheet before pigment printing. As an example of the method for providing the hydrophilic group, there is a method using low-temperature plasma with oxygen gas or the like.

In the above description, the first colored portion serving as the interference coloring surface on the fiber sheet forms a ground portion, and the second colored portion serving as a print layer forms a pattern portion. However, in the present invention, the first color forming surface serving as an interference coloring surface is used.
It is a matter of course that the color-forming portion may form a pattern portion (that is, the pattern portion serves as an interference color-forming surface) and the second color-forming portion forms a ground portion. In the latter case, the print layer forming step in each of the steps (1) to (6) for forming the print layer is omitted, and only the pattern portion of the sheet has a light reflectance of 20 to 50%. If the sheet is calendered using such an embossing roller, a target sheet can be obtained.

In the present invention, the reflectance is obtained by using a spectrophotometer to obtain a reflection curve at a wavelength in the visible light region (380 to 780 nm) of the sample. To see the reflectance with
When the light reflectance at the same wavelength is compared between the light interference coloring surface serving as the first coloring portion and the printing surface serving as the second coloring portion, for example, the difference between them is larger. ,
The second colored portion rises and looks beautiful.

[0028]

The present invention will be described in more detail with reference to the following examples. Example 1: A plain woven fabric is prepared using a polyester 75dr / 36f false twist yarn as a warp and a polyester 50dr / 36f strong twist yarn (2000T / M) as a weft. For 1 minute. << Preparation of Light Interference Fabric (First Colored Portion) >> The above woven fabric was set in a sputtering apparatus having a high frequency power supply of 13.56 MHz manufactured by Shibaura Seisakusho Co., Ltd., and evacuated to 2 × 10 ⁻³ Pa. Using stainless steel as a target,
As a gas, argon gas was introduced into the tank at a flow rate of 20 cc / min, and the degree of vacuum in the tank was controlled at 3 × 10 ⁻¹ Pa.
Then, sputtering was performed for 5 minutes at an output of 200 W from a high-frequency power source to form a 0.1 μm stainless thin film on the surface of the fabric (the above-described treatment step B—formation of first-layer metal thin film).

The woven fabric was taken out of the sputtering apparatus and then calendered. Processing conditions are metal-
Using a metal roll-type calender, the roll temperature was set to 130 ° C. and the time during which the woven fabric was held between the rolls was set to 1 second to obtain a metal thin film having a surface reflectance of 32% (the above-mentioned). Processing step A).

Next, the woven fabric after the calendering process is processed into a bell jar type 13.56 using the metal thin film surface as a treated surface.
It was set in a plasma processing apparatus having a high-frequency power supply of MHz, evacuated to 10 ^-2 Torr, and 5 cc / vinyltrimethoxysilane monomer (refractive index: 1.39) was placed in the tank.
The flow rate was controlled at 0.3 Torr in the flow tank at a flow rate of 1 minute, and plasma polymerization was performed at an output of 1 w / cm ² for 3 minutes.
A plasma polymerized thin film layer of 0.26 μm was formed (the above-mentioned processing step C—formation of second layer plasma polymerized thin film layer). At this point, when the fabric was viewed from directly above, a beautiful pink-colored interference color appeared on the entire surface.

<< Preparation of Second Color-Forming Portion >> Using the above-mentioned cloth, a pigment (Re
d NF: Dai Nippon Ink) and a printing agent in which a self-crosslinking type binder (Unibinder 221: Unichemical Co., Ltd.) was mixed to carry out printing to form a polka dot print layer. The process is printing → drying (100 ° C, 1
Min) → curing (170 ° C., 2 minutes).

When the fabric obtained in this example is viewed from the light interference surface, the ground portion (first color-developed portion) in which a bright and clear interference color of pinkish color appears on the entire surface and the ground portion It was possible to obtain an unusually unique fabric consisting of a very bright red polka dot print pattern (second colored portion) placed on the top. When the surface reflection of this cloth was measured, the interference coloring surface (first coloring portion) was 25% at 400 nm, 35% at 500 nm, 28% at 600 nm, and 7%.
It was 28% at 00 nm. The reflectance of the portion printed in red with the pigment (the second colored portion) is 1 at 400 nm.
0%, 7% at 500 nm, 15% at 600 nm, 700
It was 68% in nm. The measurement of the reflectance was performed by a self-recording spectrophotometer U-3400 (Hitachi).

Comparative Example 1: Using the woven fabric under the same conditions as used in Example 1, a metal thin film layer was formed on the surface of the woven fabric in the same manner as in Example 1, and thereafter the calendering performed in Example 1 was not performed. An organic plasma polymerized thin film layer was formed on the first layer thin film under the same conditions as in Example 1 to obtain a light interference coloring fabric. However, the interference coloring of the interference coloring fabric was dark pink, and the interference color was not bright and vivid.
Next, the same pigment print processing as in Example 1 was performed on the light interference coloring surface of this cloth.

The obtained fabric is a dark dull ground where the ground portion does not exhibit the effect of light interference coloring as described above, and the printed portion of the polka dots placed on the ground portion is also from the ground portion having no vividness. It was an ordinary thing that did not stand out.
When the surface reflection of the cloth in this case was measured, the interference coloring surface (first coloring portion) was 11.3% at 400 nm,
18.1% at 500 nm, 17.6% at 600 nm, 7
It was 19.7% at 00 nm. The reflectance of the portion printed in red with the pigment (the second color-developed portion) is 400 nm.
10.5% at 500 nm, 8.2% at 500 nm, 1 at 600 nm
5.8%, 72% at 700 nm.

Example 2: Using the same plain fabric as in Example 1, forming a first stainless steel thin film layer having a thickness of 0.1 μm under the same conditions, and forming a plasma polymerization silane of a second layer having a thickness of 0.26 μm. Although a thin film layer was formed, the calendering performed after the formation of the first metal thin film layer was different from calendering the entire woven fabric in the case of Example 1; The calendering was performed using the roll (that is, the convex portion was formed to have a pattern). However, the calendering condition is that the roll temperature is 160 ° C., and the time during which the woven fabric is held in contact with the metal roll is 2 hours.
It was set to be seconds.

The obtained fabric has a light interference coloring surface (second coloring portion) in which the ground portion is dark, and a bright pink with a polka dot pattern formed therein with a smoother surface (given by a calender roll). Interference color development of color appeared (first color development part), which seemed to be a very beautiful printed fabric. The reflectance in the visible light region of the ground portion (second colored portion) of this cloth is 11% at 500 nm,
The polka dot (first colored portion) has a thickness of 3 at 500 nm.
5%.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI // D06M 101: 30 D06M 11/00 F

Claims (1)

(57) [Claims] At least one side of a base fiber sheet has a metal thin film layer having a thickness of 0.02 to 0.2 μm and a refractive index of 1.35 to 2.00 and a thickness of 0.3 mm outside the metal thin film layer. 05
And a organic three-dimensionally crosslinked film layer of ～1Myuemu, moreover a first color partial reflectance of light is calendered fall within the scope of 20% to 50% in the visible light region, the reflectance is first And a second color-forming portion different from that of the color-forming portion.