JP3198768B2 - Sheets with interference colors - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet having interference colors. More specifically, the present invention relates to a sheet material having a single hue color and an interference color of two or more hue colors without requiring dyeing or coloring based on coloration.

[0002]

2. Description of the Related Art A light reflecting film, a metal compound transparent film, and a semi-transparent metal vapor-deposited film are laminated on one surface of a fiber cloth by the applicant of the present invention. A sheet-like material having an interference color in which a color change in hue depending on a viewing angle has been proposed and has been already known (Japanese Patent Application Laid-Open No. 3-82881). However, the material of the reflective metal film deposited here has a problem that the deposited three-layer structure film is liable to crack from the reflective metal film due to friction or bending.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a three-layer film having an interference color which is less likely to fall off due to friction and bending of the three-layer structure film and which has excellent durability. It is to provide a sheet-like material.

[0004]

The present invention has the following configuration in order to achieve the above object.

That is, in a sheet-like object having an interference color in which a reflective metal film, a transparent metal compound film, and a translucent metal film are sequentially laminated on at least one surface of the sheet-like object from the sheet-like object side, The film is Ti, Ni, C
A sheet-like material having an interference color, comprising at least one selected from o and Pt.

In a sheet-like object having an interference color in which a translucent metal film, a transparent metal compound film, and a reflective metal film are sequentially laminated on one side of the sheet-like object from the sheet-like object side, the reflective metal film Is a sheet-like material having an interference color, which is made of at least one selected from Ti, Ni, Co, and Pt.

Hereinafter, the present invention will be described in detail.

[0008] The present invention relates to Japanese Patent Application Laid-Open No. 3-828, which was previously proposed.
In order to improve the durability of the interference coloring film having a three-layer structure disclosed in Japanese Patent Publication No. 81, the composition of the interference coloring film was examined in detail, and the interference coloring film was composed of at least one material selected from Ti, Ni, Co, and Pt. The inventors have found that it is important for the reflective metal film to have the structure of the interference coloring film in order to improve the durability of the interference coloring film, and have reached the present invention.

Table 1 shows the film durability (film strength) of the interference coloring film using the reflective metal film made of each material. As shown in Table 1, target high washing resistance and wear resistance can be obtained only when Ti, Ni, Co, and Pt of the present invention are used.

[0010]

[Table 1] The test conditions shown in Table 1 were as follows: a reflective metal film / transparent metal compound film / semi-transparent metal film was deposited by induction heating vacuum deposition. The thickness of the following reflective metal film is 7
0 nm, the transparent metal compound film (SiO) was 100 nm, and the translucent metal film (Cr) was 5 nm. After each deposition, heat treatment was performed at 170 ° C for 2 minutes to increase the strength of the deposited film, and a dimethylpolysiloxane-based silicone was further applied thereon as a protective film, and heat treatment was performed at 130 ° C for 2 minutes. Was evaluated using

Deposition film (reflective metal film / transparent metal compound film /
Translucent metal film): Level 1 Al / SiO / Cr level 2 Cu / SiO / Cr level 3 Cr / SiO / Cr level 4 Ti / SiO / Cr level 5 Ni / SiO / Cr level 6 Co / SiO / Cr level 7 Washing resistance of Pt / SiO / Cr film: JIS-L-1096 Abrasion resistance by L-5 method: JIS-L-0849 Type II sheet-like material: Plain fabric using polyester filament (Example 1 and later) The same thing)

Hereinafter, the present invention will be described in more detail.

The fiber cloth of the present invention may be, for example, a known knitted or woven fabric, a non-woven fabric or a prepreg in which fibers are arranged.

The fibers constituting these fabrics include synthetic fibers (polyester, polyamide, polyacryl, vinylon, rayon, etc.), natural fibers (silk, cotton, hemp, etc.), glass fibers, inorganic fibers and the like. . Also,
Either long fiber or short fiber may be used, preferably long fiber is used, and when lightness is to be increased, it is preferable to carry out calendering.

FIG. 1 is a schematic view showing a laminated state of each thin film as an example of a sheet-like material according to the present invention.

As shown in FIG. 1, the sheet-like object having the interference color of the present invention has a reflective metal film 2, a transparent metal compound film 3, a transparent metal compound film 3 on at least one side of a sheet-like object 1 from the sheet-like object side.
The translucent metal films 4 are sequentially laminated.

On the other hand, a sheet having an interference color in which an interference coloring film is formed by sequentially laminating a translucent metal film, a transparent metal compound film, and a reflective metal film from the sheet-like material side (laminated in the reverse order of the lamination order in FIG. 1). It may be a shape. In particular, when a transparent material is used as the sheet material, the interference color development can be seen through the transparent sheet material.

FIG. 2 is a schematic diagram showing a laminated state of each thin film of another example of the sheet-like material according to the present invention. That is,
The sheet material having the interference color of the present invention may have an adhesive layer 5 interposed between the sheet material 1 and a film having a three-layer structure. By providing such an adhesive layer 5, the peel strength of the three-layer structure film from the sheet-like material 1 can be increased, and the durability of the three-layer structure film can be increased.

Further, in order to improve the durability of coloring,
It is also effective to coat a protective film that is close to the refractive index of the thin film material and has high transparency on the surface of the laminated three thin films. Such a protective film not only protects the thin film, but also reduces the amount of surface reflection from the fabric surface, and further makes the interference color deeper.

Next, a description will be given of a thin film constituting a laminated film exhibiting interference coloring.

In the present invention, the material of the reflective metal film is T
It is important that at least one selected from i, Ni, Co, and Pt is used. These reflective metal films have an average reflectance Rp _3av in the visible light region of 50.
% Or an average transmittance T _3av of 50% or less. More preferably, the reflectance average value R
p _3av is 90% or more, or transmittance average T _3av is 1
0% or less.

The material of the transparent metal compound film is Si
O, SiO ₂ , In ₂ O ₃ , TiO, TiO ₂ , indium tin oxide (ITO), MgF ₂ , Al ₂ O ₃ , Sn
At least one selected from O ₂ is preferably used. These transparent metal compound films _preferably have an average reflectance Rp _2av of 60% or less and an average transmittance T _2av of 40% or more in the visible light region. More preferably, the average reflectance Rp _2av is 30% or less,
The average transmittance T _2av is 70% or more.

Further, as a material of the translucent metal film, at least one selected from Ti, Ni, Co, Pt, Cr and Si is preferably used. These semi-transparent metal film preferably reflectance average Rp _1AV in the visible light region is 40% or less, or transmittance mean T _{1a v} is 60% or more. More preferably, the reflectance average value Rp _1av
Is 20% or less, and the average transmittance T _1av is 80% or more.

FIG. 3 shows the reflected light R ₁ , R ₂ , and the reflected light in the reflective metal film 2, the transparent metal compound film 3, and the translucent metal film 4, respectively.
FIG. 4 is an explanatory diagram illustrating R ₃ .

[0025] In FIG. 3, in the light R incident from the surface in the present invention, some of resulting reflected light R ₁ is reflected and partly transmitted through the semi-transparent metal film 4 in the transmittance T ₁ To reach the transparent metal compound film 3. The light intensity of the incident light R is I
_0, the a to reach the _{(I 0 × T 1/100} ) light transparent metal compound film 3 having a strength. Then similarly, resulting reflected light R ₂ is reflected part by the surface of the transparent metal compound film 3 and partly reaches through the transparent metal compound film 3 in the transmittance T ₂ to the reflective metal film 2 I do. That is, (I
₀ × T _1/100 × light having an intensity of T _2/100) is to reach the reflective metal film 2. And the reflective metal film 2
Some of the light that has reached reflects resulting reflected light R _3, and partly transmitted through the reflective metal film 2 in transmittance T ₃ in.

Therefore, assuming that the light intensities of the reflected light R ₁ , the reflected light R ₂ and the reflected light R ₃ are I _R1 , I _R2 and I _R3 , the reflectance is defined as follows.

The reflectance Rp ₁ [%] of the translucent metal film = 10
0 × I _R1 / I ₀ Rp ₂ [%] of transparent metal compound film = 100 × I _R2 / (I
_{0 × T 1/100) Rp} 3 [%] of the reflective metal film _{= 100 × I R3 / (I} 0 × T
_{1/100 × T 2/100} )

In the present invention, the average reflectance Rp _1av of the translucent metal film is the average reflectance Rp ₁ of the transparent metal compound film.
It is desirable close to the minimum in order to increase the reflectivity power of reflectance average Rp _3Av of _2AV and reflective metal film, Rp _2AV, the reflecting action to the extent that attained balanced reflectivity power of Rp _3Av Have Further, it is preferable that the reflectance average value Rp _3av is total reflection.

Further, the transmittance average value T _{1av of the} translucent metal film.
Is desirably as high as possible in order to increase the reflectance power of the average transmittance T _2av of the transparent metal compound film and the average reflectance Rp _3av of the reflective metal film, and the average transmittance T _2av is , Average reflectance Rp _2av , average reflectance R
It has a transmitting action in a range where the reflectance power of p _3av can be balanced. In addition, it is desirable that the transmittance average value T _3av is close to the minimum in order to increase the reflectance average value Rp _3av .

Next, the principle of interference color development in the present invention will be schematically described.

The interference by the laminated film of the sheet-like material of the present invention is roughly classified into three types of interference mechanisms.

The interference due to the reflection of the transparent metal compound film surface of the reflection and middle of the semi-transparent metal film surface of the upper layer (R ₁ and interference with R ₂₎ reflective metal film surface of the reflection and the underlying semi-transparent metal film surface of the upper layer Due to reflection of light (interference between R ₁ and R ₃ ) Interference due to reflection of the transparent metal compound film surface of the middle layer and reflection of the lower reflective metal film surface (interference between R ₂ and R ₃ ) Since the thickness of the translucent metal film is very small, almost no interference occurs and can be ignored.

On the other hand, since the interference power has a large reflectance power, the interference color becomes an interference color, and the interference color becomes a plus form, and the interference color appears strongly.

When the thickness of the surface of the transparent metal compound film in the middle layer is small, the color becomes monochromatic, but when the thickness of the semi-transparent metal compound film in the middle layer increases (for example, 20 nm or more), there is directionality. A two-hue color or more interference color.

By controlling the thickness of the transparent metal compound film in the middle layer to a predetermined thickness, desired monochromatic colors, for example, blue, green, yellow, and red can be developed. By increasing the thickness, a two-hue color is obtained.

Although the thickness of the reflective metal film depends on the material of the reflective metal film, the thickness is preferably 30 nm or more from the viewpoint of _{setting the} average reflectance Rp _3av to 50% or more. It is preferably 70 nm or less from the viewpoint of preventing cracking.

The three-layered thin film may be provided on the entire surface of the sheet-like material, but is not necessarily required, and may be provided partially.

For example, when an interference coloring film is provided on at least a part of the exposed surface of the fiber exposed on at least one surface of the fiber cloth, a sheet having an interference color on a part of the surface is obtained. When the interference coloring film is applied to a convex portion of the surface, a tip of hair, or the like, a sheet-like material having a partially interference color can be obtained from a cloth or a napped article having irregularities.

It is also possible to adopt a mode in which the portions having interference colors are arranged in a print-dyed pattern.

In short, it is sufficient that the minimum area of the surface portion that generates interference color is an area that can recognize the interference color visually.

FIG. 4 shows spectral characteristics showing the relationship between regular reflection and diffuse reflection of a fiber cloth.

FIG. 5 shows spectral characteristics showing the relationship between regular reflection and diffuse reflection of a film.

In the case of a fiber cloth, as shown in FIG. 4, the difference between specular reflection and diffuse reflection is small, and the spread of diffuse reflection light is large. This means that, as shown in FIG. 6, the diffusely reflected light is diffusely reflected radially with respect to the incident light, and spreads in an elliptical shape. That is, since the fiber surface has a curvature surface as shown in FIG. 8, the reflected light r ₁ , r ₂ ,
r ₃ and r ₄ diffuse radially. Moreover, in reality, the light is diffusely reflected more complicatedly by a large number of incident lights from various angles. For this reason, even if the viewing angle changes, the color shine does not change so much without decreasing.

In the case of a film, there is only regular reflection as shown in FIG. This means that, as shown in FIG. 7, specular reflection light having a reflection angle of 45 ° with respect to the incident light is strong, and there is almost no diffuse reflection. That is, as shown in FIG. 9, even if there are a large number of incident lights, the specularly reflected lights r ′ ₁ , r ′ ₂ ,
r _'3, r' is because it is seen as a ₄ only. Also,
Any deviation from the position of the specularly reflected light greatly changes the brightness of the color.

Next, the production method of the present invention will be described for a fiber cloth.

Examples of the fiber cloth of the present invention include known knitted and woven fabrics, as well as non-woven cloth and fibers, such as prepreg.

Examples of fibers constituting these fabrics include synthetic fibers (polyester, polyamide, polyacryl, vinylon, rayon, etc.), natural fibers (silk, cotton, hemp, etc.), glass fibers, inorganic fibers, and the like. Further, there may be mentioned a composite yarn of the above-mentioned yarns, a mixed shrinkage difference mixed yarn and the like. Further, either long fibers or short fibers may be used, but long fibers are preferred. To increase the brightness, it is preferable to perform a calendar process.

The fiber cloth may be either a woven or knitted fabric. In the case of woven fabrics, plain woven fabrics, satin, twill and other variable texture woven fabrics, desin, georgette, palace strong twisted woven fabrics, fabrics having irregularities on the surface, napped products, etc. Those that exhibit different interference colors are obtained. Furthermore, when a transparent woven fabric or a dyed woven fabric is used, it is possible to obtain a sheet having an interference color having a different effect due to the interaction with the transparency and the color of dyeing.

Further, the sheet-like material of the present invention may be a composite sheet in which a fiber fabric is laminated on a film-like material.

The sheet-like material of the present invention is obtained by first performing a desired preliminary treatment such as removing the finishing oil agent by scouring, smoothing the surface by calendering, and then applying a thin film to the surface of the fiber cloth. is there.

As a specific example, an adhesive is applied to at least one side of the fiber cloth, preferably between the fiber cloth and the three-layer structure film in order to increase the peel strength of the three-layer structure film from the fiber cloth. Then, the reflective metal film, the transparent metal compound film, and the translucent metal film are adjusted so as to have a predetermined film thickness, and are sequentially deposited (or vice versa).

When the film is heat-treated at 130 ° C. or more, more preferably 170 ° C. or more, preferably after the vapor deposition, the upper layer film becomes an oxide film, the film strength is improved, and the interference color of the fiber cloth becomes more vivid. It can be. This also prevents the oxidation of the upper layer film due to aging, which causes a change in the refractive index, and prevents the interference color from changing as a result.

In order to protect the thin film, after the heat treatment for vapor deposition, a protective film may be coated on the thin film if necessary.

The fiber cloth having interference colors of the present invention is used in the field of clothing such as sportswear, casual wear, stage costumes, pantyhose, tights, shirts, blouses, scarves, ties, ribbons, belts, etc., futon covers, curtains and rugs. , Stage curtain, banner, wrapping ribbon,
Excellent versatility for bedding such as one-point marks, umbrellas, handbags, interior goods, and daily necessities.

When a film is used as the sheet-like material, a vapor-deposited film may be provided on the film surface as described above.

[0056]

The present invention will be described more specifically with reference to the following examples.

Example 1 A polyester filament yarn (warp 50 denier × 18 filaments, weft 75 denier × 36 filaments) was plain woven (vertical 110 / inch,
After scouring and finishing the woven fabric having a width of 81 lines / inch, Ti was deposited as a reflective metal film on one surface of the woven fabric so as to have a thickness of 70 nm, and four types of these were prepared.

On the four kinds of reflective metal films, SiO was deposited by an induction heating vacuum vapor deposition method so as to have a film thickness of 100 nm, 120 nm, 150 nm, and 200 nm, respectively, and a transparent metal compound film was laminated.

Next, the film thicknesses of 100 nm, 120 nm, 150
5 nm thick Cr on 200 nm and 200 nm transparent metal compound film
And a semi-transparent metal film was laminated.

Thereafter, in order to increase the strength of the film, 170 ° C. ×
Heat treated for 2 minutes.

Further, a dimethylpolysiloxane-based silicone was applied thereon as a protective film, and heat-treated at 130 ° C. for 2 minutes.

As shown in Table 2, the obtained fiber fabric developed a remarkably clear single hue color due to the light interference phenomenon. And what was excellent in durability, such as washing resistance and abrasion resistance, was obtained.

[0063]

[Table 2] [Example 2] In the same manner as in Example 1, except that Ni was deposited so as to have a thickness of 70 nm as a lower reflective metal film, vapor deposition, heat treatment, and protective film lamination were performed under the same conditions as in Example 1.

As shown in Table 3, the obtained fiber fabric developed a remarkably clear single hue color due to the light interference phenomenon. And what was excellent in durability, such as washing resistance and abrasion resistance, was obtained.

[0065]

[Table 3] [Example 3] Polyester filament yarn (50 denier-12 filament) supplied at a yarn speed of 525 m / min
Then, a polyester filament yarn (100 denier × 96 filaments) supplied at a yarn speed of 600 m / min was gathered, and the fluid mixing treatment was drawn at 500 m / min to obtain a yarn with a difference in yarn length. A reflective metal film, a transparent metal compound film, and a semi-transparent metal film were sequentially deposited, heat-treated, and a protective film lamination process were performed on one surface of the yarn length difference mixed fiber fabric under the same conditions as in Example 1.

As shown in Table 4, the obtained fiber fabric developed a remarkably clear single hue color due to the light interference phenomenon. And what was excellent in durability, such as washing resistance and abrasion resistance, was obtained.

[0067]

[Table 4] [Example 4] Polyester filament yarn (warp 50 denier-24 filament; approximately triangular section fiber, weft 75)
A taffeta using a denier-72 filament; a fiber having a substantially round cross section) is prepared and drawn to produce a fabric having an uneven surface, and the same condition as in Example 1 is applied to one surface of the fabric having the uneven surface. With reflective metal film, transparent metal compound film,
A translucent metal film was sequentially deposited, heat-treated, and laminated with a protective film.

As shown in Table 5, the resulting fabric exhibited a remarkably clear, deep and varied color due to the light interference phenomenon. And what was excellent in durability, such as washing resistance and abrasion resistance, was obtained.

[0069]

[Table 5] [Example 5] A woven fabric (warp: about 100 / inch) using a super bright yarn of polyester filament (warp: 200 denier-10 filament, substantially round section fiber, weft: 400 denier-20 filament, substantially round section fiber) ,
Weft: about 95 yarns / inch, texture: plain weave), a finishing set is applied to prepare a transparent cloth, and a semi-transparent metal film, a transparent metal compound film,
Except for the order of the reflective metal films, the layers were laminated by the induction heating vacuum deposition method in the same manner as in Example 1.

The translucent metal film was made of Cr and had a thickness of 3 nm. The transparent metal compound film is composed of SiO and has a thickness of 80 nm, 100 nm, 120 nm, and 150 nm, respectively.
Was created. The reflective metal film was made of Ti and had a thickness of 80 nm. After the translucent layer, the transparent layer, and the reflective layer are sequentially deposited, heat treatment is performed at 170 ° C. for 2 minutes, and a polydimethylpolysiloxane-based silicone is further coated thereon as a protective film.
The heat treatment was performed under the conditions of minutes.

The resulting fabric having a transparent layer having a film thickness of 80 nm has a deep color mainly composed of blue and has a film thickness of 10 nm.
The one with 0 nm gives a deep color mainly composed of green,
With a film thickness of 120 nm, a deep color mainly composed of yellow was obtained, and with a film thickness of 150 nm, a deep color mainly composed of red was obtained.

The obtained transparent fabric changes its color intricately depending on the viewing angle, and at the same time, exhibits excellent sheer feeling and weaving feeling. A high-grade color tone is obtained, and washing resistance and abrasion resistance are obtained. And the like having excellent durability.

[0073]

The fiber fabric having an interference color according to the present invention has the following effects.

(1) The material of the reflective metal film is Ti, Ni,
By using Co and Pt, a strong three-layer structure film can be formed, and high washing resistance and abrasion resistance can be obtained.

(2) A single hue color and a two-hue color can be freely obtained by a light interference phenomenon without using a dye.

(3) High hue and high chroma, which cannot be obtained with conventional dyes and pigments, and even when two or more hue colors are obtained, each hue is independent and does not become dark.

(4) Depending on the adjustment of each film thickness and the viewing angle,
Various interference colors can be developed.

(5) The metallic luster can be sharply developed by the heat treatment.

(6) No fading at all.

(7) The fiber fabric is excellent in versatility for clothing, interior use, industrial materials and the like, since the original function of the fiber such as moisture absorption and air permeability is not impaired.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a laminated state of each thin film as an example of a sheet-like material according to the present invention.

FIG. 2 is a schematic diagram showing a laminated state of each thin film of another example of the sheet-like material according to the present invention.

FIG. 3 is an explanatory diagram illustrating reflected light from each film laminated on a sheet according to the present invention.

FIG. 4 is a spectral characteristic showing a relationship between regular reflection and diffuse reflection of a fiber cloth.

FIG. 5 is a spectral characteristic showing a relationship between specular reflection and diffuse reflection of a film.

FIG. 6 is a reflection distribution diagram of the fiber cloth according to the present invention.

FIG. 7 is a reflection distribution diagram of the film according to the present invention.

FIG. 8 is a diagram showing a reflection mechanism of a fiber cloth.

FIG. 9 is a diagram showing a film reflection mechanism.

[Explanation of symbols]

1: sheet 2: reflective metal film 3: transparent metal compound film 4: semitransparent metal film 5: adhesive layer R: incident light R _1, R _2, R _3: reflection light T _1, T _2, T ₃ : Transmittance d ₁ , d ₂ , d ₃ : film thickness r ₁ , r ₂ , r ₃ , r ₄ : diffuse reflection light r ′ ₁ , r ′ ₂ , r ′ ₃ , r ′ ₄ : regular reflection light

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI // D06M 101: 32 (56) References JP-A-3-82881 (JP, A) JP-A-61-15962 (JP, A) JP JP-A-61-132676 (JP, A) JP-A-6-93566 (JP, A) JP-A-5-156575 (JP, A) Japanese Utility Model Showa 62-199183 (JP, U) (58) Fields investigated (Int) .Cl. ⁷ , DB name) B32B 1/00-35/00 D06M 11/83

Claims (10)

(57) [Claims] 1. A sheet-like object having an interference color in which a reflective metal film, a transparent metal compound film, and a translucent metal film are sequentially laminated on at least one surface of the sheet-like object from the sheet-like object side. A sheet-like article having an interference color, wherein the film is made of at least one selected from Ti, Ni, Co, and Pt. 2. A sheet-like article having an interference color in which a translucent metal film, a transparent metal compound film, and a reflective metal film are sequentially laminated on one side of the sheet-like article from the sheet-like article side. Is a sheet-like material having an interference color, wherein the sheet-like material is made of at least one selected from Ti, Ni, Co, and Pt. 3. The method according to claim 1, wherein the transparent metal compound film is made of SiO, SiO ₂ ,
_{In 2 O 3, TiO, TiO} 2, indium tin oxide (ITO), claim, characterized in that it consists of MgF _2, Al ₂ O _3, at least one member selected from SnO ₂ 1
Or a sheet having the interference color described in 2. 4. A translucent metal film comprising Ti, Ni, Co, P
The sheet-like article having an interference color according to claim 1 or 2, wherein the sheet-like article comprises at least one selected from t, Cr, Al, Si, Ag, and Au. 5. The sheet-like article having an interference color according to claim 1, wherein the sheet-like article is a film. 6. The sheet having an interference color according to claim 1, wherein the sheet is a fiber cloth. 7. The sheet-like article having an interference color according to claim 6, wherein a part of the exposed surface of the fiber exposed on at least one surface of the fiber cloth has an interference color. 8. The sheet having an interference color according to claim 1, wherein the reflective metal film has a thickness of 30 nm to 70 nm. 9. reflectance average Rp _1AV 40% of a semi-transparent metal film in the visible light region below, reflectance average value of the transparent metal compound film reflectance average Rp _2AV 60% or less and a reflective metal film of Rp _3Av The sheet-like article having an interference color according to any one of claims 1 to 8, wherein the ratio is 50% or more. 10. A transmission average semi-transparent metal film in the visible light region T _1AV 60% or more, the transmittance average of the transparent metal compound transmission average value T _2AV film 40% or more and a reflective metal film T _The sheet having an interference color according to any one of claims 1 to 9, wherein _3av is 50% or less.