JPH06248573A - Vapor deposition product and its production - Google Patents

Abstract

PURPOSE:To improve the adhesive strength of a vapor deposition film and impart excellent resistance to washing and abrasion to a vapor deposition product. CONSTITUTION:This vapor deposition product comprises a vapor deposition film formed through an intermediate agent containing at least a silicone-based resin 2 and silicon dioxide on the surface of an organic substrate 1. Furthermore, this method for producing the vapor deposition product is to produce the silicon dioxide by plasma treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vapor-deposited product and a method for producing the same, and more particularly to a vapor-deposited film-forming fiber product or a sheet-like product which is capable of enhancing the adhesive force of a vapor-deposited film and which is suitable for vapor deposition. The present invention relates to a product and a manufacturing method thereof.

[0002]

2. Description of the Related Art In a vapor-deposited film, for example, a fiber product or a sheet-like material having a metal vapor-deposited film formed thereon, the adhesion between the vapor-deposited metal film and the fiber or resin after the vapor deposition treatment is lower than expected.
When washing (washing with water or dry cleaning), most of the metal comes off, which is a major bottleneck in product development.

In order to improve this, a method of coating a resin with a protective film after a vapor deposition process is carried out. However, no matter how much the protective film is formed on a metal, the adhesiveness between the metal and the fiber or the resin is improved. Is not a fundamental solution due to its low value. That is, although the metal film is less likely to partially drop during washing, the metal film including the protective film is peeled off over a wide area as time passes or the number of times of washing increases.

On the other hand, a fiber cloth having an interference color in which a specific light interference film is vapor-deposited on the surface of the fiber cloth to cause interference color development was previously proposed by the present applicant and has been already known (special feature). Kaihei 3-82881).

Even in the fiber cloth having such an optical interference film deposited thereon, since the optical interference film is directly deposited on the surface of the cloth, the same problem as described above, that is, the friction and bending of the deposited optical interference film is prevented. There has been a problem that the adhesive strength may be insufficient.

[0006]

In the present invention, attention is paid to such problems, and a fiber product (fiber cloth) or a sheet-like product,
Furthermore, the purpose is to improve the adhesive strength of a vapor-deposited film vapor-deposited on the surface of the product, and ultimately to impart excellent washing resistance, abrasion resistance, etc. to the vapor-deposited product. .

[0007]

Means for Solving the Problems The vapor-deposited product of the present invention for this purpose has a metal or metal-containing material on at least a part of the surface of an organic base material via an intermediate agent containing at least a silicone-based resin and silicon dioxide. It is provided with a vapor-deposited thin film containing an inorganic substance.

Particularly, the silicon dioxide contained in the above-mentioned intermediate is optimally produced by plasma treatment.
The silicon dioxide produced by such plasma treatment is
It can exist in the vicinity of the surface of the intermediate in the activated molecular form, and can be uniformly distributed in the molecular order because it is generated by the plasma treatment, and has a high adhesive force to the deposited thin film formed thereon. In particular, when the elemental composition of the intermediate agent is plasma-treated at least in the vicinity of the thin film until the number of carbon atoms is 2 and the number of silicon atoms is 1 or more, extremely high adhesion can be obtained.

Therefore, in the method for producing a vapor-deposited product according to the present invention, in order to provide such a high adhesive force, silicone is applied to the surface of the organic base material, plasma treatment is applied thereto, and the plasma-treated surface is treated. The method comprises depositing a thin film having a metal or an inorganic substance.

More specifically, in the method for producing a vapor-deposited product of the present invention, silicone is applied to the surface of an organic base material, the silicone is heat-treated to form a silicone resin layer, and a plasma treatment is performed on the silicone resin layer. , A method of depositing a thin film having a metal or an inorganic substance on a plasma-treated surface.

That is, in the method of the present invention, a silicone film is first formed on the surface of a fiber cloth or sheet by coating or dipping, and the silicone is heat treated to form a silicone resin layer. By the plasma treatment, more precisely, the low temperature plasma treatment, the silicone resin is activated (silicon dioxide is uniformly generated in the molecular order by the plasma treatment), and a predetermined vapor deposition film is formed on the resin film. It is formed by a vapor deposition process. The adhesive force between the activated silicone-based resin film and the vapor deposition film is significantly improved, and a vapor deposition film that does not easily peel off due to friction or bending is realized.

The silicone used in the present invention may be, for example, a methylhydrogenpolysiloxane emulsion, and the catalyst may be, for example, a zinc-based one. The content of silicone is 2-1
About 0% by weight is suitable, and about 2 to 10% by weight is suitable for the zinc-based catalyst.

As a method of applying silicone to the surface of the fiber cloth or sheet-like material, for example, a dipping method can be mentioned, and an appropriate drawing ratio is about 20 to 60%. The conditions for drying and curing after application are 160 ° C.,
A continuous condition of about 2 minutes is preferable.

The conditions of the low temperature plasma treatment are, for example, vacuum degree: 20 to 100 Pa and discharge power: 2 to 7K.
V, processing speed: about 5 to 30 m / min is suitable. The treatment atmosphere may be the air or a gas atmosphere of oxygen, argon or the like. Both sides may be processed, or at least the surface to be vapor-deposited may be processed.
The degree of low-temperature plasma treatment needs to be changed depending on the chemical composition of the silicone-based resin, but from the viewpoint of effect, the elemental composition of the silicone-based resin layer should be such that at least in the vicinity of the vapor-deposited film, 1 atom of silicon atom to 2 atoms of carbon atom The above is preferable in terms of adhesiveness.

The substrate used in the present invention is not particularly limited as long as it is an organic substrate, and is, for example, a fiber cloth or a sheet. The fiber cloth is not particularly limited, and may be a thin cloth to a thick cloth. Examples of the sheet material include plastic film and paper.

The vapor deposition material is not particularly limited and includes metals, inorganic substances, oxides, nitrides and the like.

The metals used as the vapor deposition material include Al, Au, Cr, Cu, Mg, Ni and Ti, and the inorganic material includes Si. Further, as oxides, Al ₂ O ₃ , In ₂ O ₃ , Cr ₂ O ₃ ,
Examples thereof include MgO, SiO, SiO ₂ and TiO ₂ , and examples of the nitride include AlN, TiN and Si ₃ N ₄ .

The layer structure of the vapor deposition film may be a single layer or a laminated structure.

Such a vapor deposition film is vapor-deposited on the silicone resin film which has been subjected to the low temperature plasma treatment as described above. Then, as described above, a strong adhesive force is exhibited between the activated silicone-based resin film and the activated silicone-based resin film. Good adhesiveness is originally secured between the silicone resin film and the organic base material. The vapor deposition method is not particularly limited, and for example, a method in which the base material is placed in a known thin film forming apparatus such as a vacuum vapor deposition apparatus, a sputtering apparatus, an ion plating apparatus and the vapor deposition film is formed under reduced pressure is preferable. .

The strengthening of the adhesive force is achieved by forming a low temperature plasma-treated silicone-based resin film, and other resin films cannot achieve the target high adhesive force. X-ray photoelectron spectroscopy can be used for the atomic state analysis of the silicone resin film surface. Further, Auger electron spectroscopy can be used for elemental composition (ratio of the number of atoms) analysis. Further, in the case where the vapor-deposited film is formed, a method of analyzing the film while digging down the film can be used in combination with the ion etching method.

As shown in Table 1 by comparing the durability with each resin and with and without plasma treatment, the silicone resin, which is also a low temperature plasma treatment, has a target high durability. Washability and abrasion resistance can be obtained.

[0022]

[Table 1]

The conditions of the test shown in Table 1 are as follows. Deposition film: Al / SiO / Cr Washing resistance of film: JIS-L-1096 Wear resistance by L-5 method: JIS-L-0849 Type II cloth used: Plain woven fabric using polyester filaments (Examples described later) The same as 1)

The vapor deposition product of the present invention and the method for producing the same are
It can also be applied as a pretreatment when depositing an electromagnetic interference film, for example, an optical interference film. That is, it can also be applied when a fiber cloth or sheet-like material having an interference color is obtained by vapor deposition of the light interference film.

In the fiber cloth or sheet having this interference color, the above-mentioned silicone resin film is formed,
After it is subjected to a low temperature plasma treatment, an optical interference film is deposited thereon.

This optical interference film can take the following various modes. First, when the light interference film is composed of only a transparent layer, as shown in FIG. 1, a transparent layer 3, such as a transparent layer, is formed on a silicone resin film 2 on one or both sides of a substrate 1 made of a fiber cloth or a sheet. The transparent layer 3 made of a metal compound film is provided by vapor deposition.

In the base material 1 on which such a transparent layer 3 is laminated, the light R incident from the front surface side is reflected light R ₂ on the front surface of the transparent layer 3 and reflected light R ₃ on the rear surface, that is, transparent. Color is developed by the interference between the layer and the reflection at the interface between the transparent layer and the substrate (or the silicone resin film 2) adjacent to the transparent layer.

This color development changes variously depending on the material of the transparent layer 3, the color of the substrate 1 itself, and the thickness of the transparent layer 3. Especially,
In order to obtain a brilliant color, the thickness of the transparent layer 3 is 40
It is preferably 0 Å or more and 5000 Å or less.

Alternatively, the optical interference film may be formed by a two-layer structure in which the reflective layer 4 and the transparent layer 3 are sequentially laminated from the base material 1 side as shown in FIG. The reflective layer 4 is made of, for example, a metal thin film having an average reflectance of 60% or more (preferably 90% or more) in the visible light region, and examples of the material of the reflective metal film include Al, Cu, Ag, and M.
At least one selected from g, Au, Cr, Pe and Rh can be mentioned. Such a reflective layer 4 can also be provided by vapor deposition, and the thickness of the reflective metal film forming the reflective layer 4 is preferably 500 Å or more.

In the base material 1 in which the reflective layer 4 and the transparent layer 3 are sequentially laminated, the light R incident from the front side is
The reflected light R ₂ on the front surface of the transparent layer 3 and the reflected light R ₃ on the rear surface, that is, the reflected light on the boundary surface between the transparent layer 3 and the reflective layer 4 interfere with each other to develop a color.

As shown in FIG. 3, the light interference film includes the reflective layer 4, the transparent layer 3 and the semitransparent layer 5 from the side of the substrate 1.
May be formed by sequentially stacking and in this order to form a three-layer structure. The semitransparent layer 5 is made of, for example, a semitransparent metal film having an average reflectance of 60% or less in the visible light region, and the material of the semitransparent metal film is Al, Cu, A.
At least one selected from g, Mg, In, Cr, Si, Au, and Au / Pt can be used. Such a semitransparent layer 5 can also be provided by vapor deposition, and the thickness of the semitransparent metal film forming the semitransparent layer 5 is preferably 20 Å or more and 500 Å or less.

In the base material 1 in which the reflective layer 4, the transparent layer 3 and the semitransparent layer 5 are laminated in this order, the light R incident from the front side is the surface of the semitransparent layer 5 and the surface of the transparent layer 3. , Reflected light R ₁ on the front surface of the reflective layer 4 (back surface of the transparent layer 3),
R ₂ and R ₃ are generated, and the reflected lights R ₁ , R ₂ and R ₃ interfere with each other to develop an interference color.

Further, the optical interference film is, as shown in FIG.
It may be formed by forming a two-layer structure in which the transparent layer 3 and the semitransparent layer 5 are sequentially laminated from the base material 1 side. In such a base material 1, a color is produced mainly by the interference between the reflected lights R ₂ and R ₃ .

Although not shown, a protective film may be provided on the surface of the light interference film by coating or the like, if necessary. The protective film is preferably substantially transparent so as not to impair the incidence of light on the light interference film and the development of the interference color from the light interference film. However, it may be colored.

[0035]

EXAMPLES Specific examples will be described below. Example 1 Polyester filament yarn (vertical 50 denier x 18)
Filament, approximately round cross-section fiber and horizontal 75 denier × 36
Filament, approximately circular cross-section fiber) plain weave (110 warp /
After refining the woven fabric made into inch, width 81 / inch), add silicone by dipping method
It was heat-treated at 0 ° C. to form a silicone resin. afterwards,
Applying low temperature plasma treatment, Al film thickness 80 on one side of the fabric
A metal film was vapor-deposited by an induction heating vacuum vapor deposition method so as to have 0Å.

The silicone-based resin used was a methylhydrogenpolysiloxane emulsion, and a zinc-based catalyst was used as the catalyst. The processing conditions by the dip method and the plasma processing conditions are as follows. Dip treatment: Silicone resin content: 7% Zinc catalyst content: 7% Dip treatment Squeeze ratio: 40% Drying and curing: 160 ° C x 2 minutes, continuous plasma treatment: Vacuum degree: 40 Pa Treatment atmosphere: Discharge in air Electric power: 5.5KV Processing speed: 20m / min Processing surface: Both sides

As a result, the A1 vapor deposition film is resistant to friction and bending.
Strengthening of adhesion with fibers was measured. In Example 1, by applying the silicone resin and then performing the plasma treatment, the washing resistance was improved from the second grade to the fifth grade and the abrasion resistance was improved from the first grade to the third grade. The conditions of the test at this time are as follows. Washing resistance: According to JIS-L-1096 L-5 method. Abrasion resistance: According to JIS-L-0849 II type.

In Example 1, the surface of the silicone resin layer before and after the low temperature plasma treatment was analyzed by X-ray photoelectron spectroscopy, and the atomic number ratio of carbon atoms and silicon atoms and Si and SiO _{2 in} silicones were analyzed. Table 2 shows the ratio of Si in the
It was shown to. From the results, it was found that the low temperature plasma treatment significantly increased silicon dioxide in the silicone resin. It is considered that the silicon dioxide generated by this plasma treatment greatly contributes to the improvement of the adhesive strength.

[0039]

[Table 2]

The X-ray photoelectron spectroscopy is a method in which the intensity of photoelectrons excited by X-rays irradiated on the sample surface and emitted from the surface is measured as a function of kinetic energy, and a photoelectron spectrum is obtained from the measured intensity. It can be used not only for elemental analysis of substances, but also for compositional analysis of substances from the peak intensity ratio of core photoelectrons. In addition, since the binding energy value of the inner-shell photoelectron varies depending on the difference in the chemical bond state even for the same element, the state analysis can be performed.

The analysis conditions of the X-ray photoelectron spectroscopy in this example are as follows. X-ray source: Mgkα X-ray output: 10 kV 20 mA Analyzer: Pass energy: WIDE SCAN 50 eV NARROW SCAN 20 eV Resolution: 1 eV Vacuum degree: ˜1 × 10 ⁻⁸ mbar Geometry: θ (escape angle) = 0 °

Example 2 High shrink polyester filament yarn (50 denier x 2
(4 filaments, approximately round cross-section fiber, boiling water shrinkage of about 20%)
And low shrinkage polyester filament yarn (50 denier ×
48 filaments, approximately triangular cross-section fibers, boiling water shrinkage of about 7
%) And subjected to fluid mixing treatment and then twisted about 200 times / m to obtain a woven fabric (warp: about 80 / inch, weft: about 100) / Inch, texture: 2/2 twill), relax treatment, set,
Alkali treatment and finishing set were applied to make a yarn length difference woven yarn fabric. Then, a silicone resin was applied by the dipping method, and dried and cured. After the plasma treatment from above, the optical interference film having the three-layer structure shown in FIG. 3 was vapor-deposited on one surface of the yarn length difference mixed fiber fabric by the induction heating vacuum vapor deposition method. The treatment conditions of the silicone resin by the dipping method and the plasma treatment conditions are the same as in Example 1.

The reflective layer is made of A1 and has a film thickness of 800 Å
The transparent layer is made of SiO and has a thickness of 80
The thickness was 0Å, 1000Å, 1200Å, 1500Å, and the semitransparent layer was composed of Cr and the film thickness was 30Å. After these reflective layer, transparent layer, and semi-transparent layer are vapor-deposited, heat treatment is performed at 170 ° C. for 2 minutes, and then polydimethylpolysiloxane-based silicone is coated thereon as a protective film.
It heat-processed on condition of 2 degreeC.

As a result, the adhesion of the lower vapor-deposited film to the fiber was measured against washing, rubbing and bending. As a result, the film thickness of the transparent layer is 8 without dropping off both the intermediate layer and the upper layer.
00 Å has a deep color mainly composed of blue, and 1000 Å has a deep color mainly composed of green, and 1200 Å has a yellow mainly composed. A deep color was obtained, and for the film having a film thickness of 1500 Å, a deep color mainly composed of red was obtained.

In Example 2, by applying the silicone resin and then performing the plasma treatment, the washing resistance was improved from the third grade to the fifth grade and the abrasion resistance was improved from the second grade to the fourth grade. The conditions of the test at this time are as follows. Washing resistance: According to JIS-L-1096 L-5 method. Abrasion resistance: According to JIS-L-0849 II type.

In the obtained yarn length difference mixed fiber fabric, the color tone changes intricately depending on the viewing angle, and the surface unevenness due to the yarn length difference mixed yarn gives a more three-dimensional and swelling feeling, and the color of each part A high-quality color tone with complex changes was obtained.

The surfaces before and after the low-temperature plasma treatment were analyzed by X-ray photoelectron analysis, and the atomic number ratio of carbon atoms and silicon atoms and the Si ratio in silicones and Si in SiO ₂ are shown in Table 3. . The results showed that the low temperature plasma treatment increased the amount of silicon dioxide in the silicone resin.

[0048]

[Table 3]

[0049]

As described above, according to the vapor deposition product and the method for producing the same of the present invention, the presence of silicon dioxide, particularly silicon dioxide produced by the plasma treatment, in the intermediate agent causes formation of a vapor deposition film. It is possible to obtain an extremely high adhesive force between them, the vapor-deposited film is not easily peeled off, and a textile product, a sheet-like product, or the like having excellent washing resistance and abrasion resistance can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic partial cross-sectional view showing an example of a base material having an interference color produced by the method of the present invention.

FIG. 2 is a schematic partial cross-sectional view of a base material having an interference color according to another example different from FIG.

FIG. 3 is a schematic partial cross-sectional view of a base material having an interference color according to yet another example.

FIG. 4 is a schematic partial cross-sectional view of a base material having an interference color according to yet another example.

[Explanation of symbols]

1 Base Material 2 Silicone Resin 3 Transparent Layer 4 Reflective Layer 5 Semi-Transparent Layer R Incident Light R ₁ , R ₂ , R ₃ Reflected Light

Claims (19)

[Claims] 1. At least a part of the surface of the organic base material,
A vapor-deposited product comprising a vapor-deposited thin film having a metal or an inorganic substance via an intermediate agent containing at least a silicone resin and silicon dioxide. 2. The vapor deposition product of claim 1, wherein the silicon dioxide is produced by plasma treatment. 3. The vapor deposition product according to claim 1, wherein the organic base material is made of polyester. 4. The vapor deposition product according to claim 1, wherein the organic base material is a sheet-like material. 5. The vapor deposition product according to claim 1, wherein the organic base material is a textile product. 6. The vapor deposition product according to claim 1, wherein the elemental composition of the intermediate agent is such that at least in the vicinity of the thin film, the number of silicon atoms is 1 or more with respect to 2 carbon atoms. 7. The vapor deposition product according to claim 1, wherein the thin film is an electromagnetic interference film. 8. The optical interference, wherein the electromagnetic interference film has a transparent layer formed of a substantially transparent thin film capable of developing color due to interference of light incident from the front surface side with light reflected on the front surface and light reflected on the back surface. The vapor-deposited product according to claim 7, which comprises a film. 9. The vapor-deposited product according to claim 8, wherein the light interference film includes only the transparent layer. 10. The light interference film is a film having a two-layer structure in which a reflective layer having an average reflectance of 60% or more in a visible light region and a transparent layer are sequentially laminated from the base material side. 8 vapor deposition products. 11. The light interference film has a reflection layer having an average reflectance of 60% or more in a visible light region, the transparent layer, and an average reflectance of 60% or less in a visible light region from the base material side. 9. The vapor-deposited product according to claim 8, which is composed of a film having a three-layer structure in which the semi-transparent layer is laminated in this order. 12. The light interference film has an average reflectance of 60% in the visible light region with respect to the transparent layer from the base material side.
The vapor-deposited product according to claim 8, comprising a film having a two-layer structure in which the following semitransparent layers are sequentially laminated. 13. A method for producing a vapor-deposited product, which comprises applying silicone to the surface of an organic base material, performing plasma treatment on the surface, and depositing a thin film having a metal or an inorganic substance on the plasma-treated surface. 14. A thin film having a metal or an inorganic substance on a plasma-treated surface, which is obtained by applying silicone to the surface of an organic base material, heat-treating the silicone to form a silicone-based resin layer, and subjecting the silicone-based resin layer to plasma treatment. A method for producing a vapor-deposited product, which comprises vapor-depositing. 15. A substantially transparent thin film capable of being colored in at least one surface of the base material by the interference of light incident from the front surface side with reflected light on the front surface and reflected light on the back surface, in the vapor deposition process. 15. The method for producing a vapor-deposited product according to claim 13 or 14, which is performed by vapor-depositing an optical interference film having a transparent layer. 16. The method of manufacturing a vapor-deposited product according to claim 15, wherein the light interference film includes only the transparent layer. 17. The light interference film is a film having a two-layer structure in which a reflective layer having an average reflectance in the visible light region of 60% or more and a transparent layer are sequentially laminated from the base material side. 15. The manufacturing method of the vapor deposition product of 15. 18. The light interference film comprises a reflective layer having an average reflectance of 60% or more in the visible light region, the transparent layer, and an average reflectance of 60% or less in the visible light region from the base material side. 16. The method for producing a vapor-deposited product according to claim 15, comprising a film having a three-layer structure in which the semi-transparent layer which is the above is sequentially laminated in this order. 19. The light interference film has an average reflectance of 60% in the visible light region with respect to the transparent layer from the base material side.
The method for producing a vapor-deposited product according to claim 15, comprising a film having a two-layer structure in which the following semi-transparent layers are sequentially laminated.