JP2003268673A - Deposited fiber structure and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a fiber structure which has excellent washing resistance and abrasion resistance. <P>SOLUTION: The deposited fiber structure wherein a deposited thin film containing a metal and/or an inorganic substance is laminated to at least one portion of the surface of the fiber is characterized in that the deposited thin film is laminated to the fiber structure through an intermediate agent containing at least an oxidized silicone-based resin and a melamine-based resin, and the deposited thin film is covered with a resin layer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vapor-deposited fiber structure and a method for manufacturing the same. Particularly, the present invention relates to a vapor-deposited fiber structure optimal for use in a vapor-deposited film-forming fiber product requiring durability by enhancing the durability of the vapor-deposited film, and a method for producing the same.

[0002]

2. Description of the Related Art In the case of a fiber cloth on which a vapor-deposited film, for example, a metal vapor-deposited film is formed, adhesion between the vapor-deposited metal film and the fibers or the resin after the vapor deposition treatment is low, and most of them are washed (washed with water or dry cleaned). Metal has fallen off and has become a major bottleneck in product development. In order to improve such a problem, Japanese Patent Laid-Open No. 58-136891 discloses a method of coating a protective film after a vapor deposition process.

However, even if the protective film is formed on the vapor-deposited metal film, the adhesiveness between the metal and the fiber or the metal and the resin is not considered, and although it is effective for temporary protection, it is fundamental. The current situation is that it has not been resolved.

[0004]

SUMMARY OF THE INVENTION In the present invention, attention is paid to these problems, the purpose is to improve the adhesive strength of the vapor deposition film to the fiber structure and to prevent the vapor deposition film from falling off. An object of the present invention is to provide a vapor-deposited fiber structure suitable for the purpose of imparting excellent washing resistance and abrasion resistance to the fiber structure and a method for producing the same.

[0005]

In order to solve the above-mentioned problems, the present invention has the following constitution.

That is, in a fiber structure in which a vapor-deposited thin film containing a metal and / or an inorganic substance is laminated on at least a part of the fiber surface, the vapor-deposited thin film is an intermediate product containing at least an oxidized silicone resin and melamine resin. The present invention relates to a vapor-deposited fiber structure which is laminated on a fiber structure via an agent and in which the vapor-deposited thin film is covered with a resin cross-linked product.

The manufacturing method of the present invention has the following constitution for solving the above-mentioned problems.

That is, a step of applying a resin containing a silicone-based resin and a melamine-based resin to the surface of the fiber structure, a step of oxidizing the surface layer of the silicone-based resin by plasma treatment, and a thin film having a metal and / or an inorganic substance are vapor-deposited. And a step of coating with a resin, the method for producing a vapor-deposited fiber structure.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The vapor-deposited fiber structure of the present invention is a fiber structure in which a vapor-deposited thin film containing a metal and / or an inorganic substance is laminated on at least a part of the fiber surface.
The vapor-deposited thin film is laminated on the fiber structure through an intermediate agent containing at least an oxidized silicone resin and a melamine-based resin, and the vapor-deposited thin film is covered with a resin.

The vapor-deposited thin film containing a metal and / or an inorganic substance means a thin film having a single-layer or laminated structure formed by various thin-film forming devices such as a vacuum vapor deposition device, a sputtering device and an ion plating device.

Examples of metals include Al, Ag, Cr,
Ni, Ti, stainless steel or the like can be used, and Si or the like can be used as the inorganic substance. Metals and inorganic substances also include oxides and nitrides thereof. Examples of oxides include Al ₂ O ₃ , Cr ₂ O ₃ , MgO, SiO,
SiO ₂ , TiO ₂ or the like can be used.

The vapor-deposited thin film may be a single layer or a laminate of a plurality of layers.

The vapor-deposited thin film being laminated on a fiber structure through an intermediate agent containing at least an oxidized silicone resin and a melamine resin means that the surface of a single fiber constituting the fiber structure is oxidized. And a melamine-based resin, and the vapor-deposited thin films are laminated and adhered via the coating film. By including the melamine-based resin, the adhesiveness of the silicone-based resin to various fiber materials can be significantly improved.

Here, it is important that the intermediate silicone resin is oxidized. Silicon dioxide is generated in the silicone resin contained in the intermediate by being oxidized by the plasma treatment, but the Si content of the generated silicon dioxide is more than twice the Si content in the silicone resin. Those that are preferable.

The silicon dioxide produced by such plasma treatment exists in the vicinity of the surface of the intermediate in the activated molecular form and has a uniform distribution on the molecular order, so that it has a high adhesive force to the deposited thin film. I think it will be. Moreover, it is preferable that the elemental composition of the intermediate agent is 1 or more of silicon atoms with respect to 2 carbon atoms in the vicinity of the deposition thin film stack. When the ratio is changed by the plasma treatment, it has an extremely high adhesive force to the deposited thin film. In this way, a material having a high adhesiveness to both the fiber and the vapor-deposited thin film and having a high drop-off resistance can be obtained by interposing the intermediate agent.

In the present invention, the vapor-deposited thin film is covered with the resin layer. The resin layer here is preferably crosslinked, and is preferably a resin crosslinked layer formed by cross-linking between polymer chains, cross-linking via a cross-linking agent, or the like.

Examples of the resin as used herein include urethane-based, acrylic-based, polyester-based, silicone-based, polyamide-based, etc., melamine-based, phenol-based, urea-based resins and the like. Of these, urethane-based, acrylic-based, and silicone-based resins are preferable from the viewpoint of texture. When the resin layer is crosslinked, an isocyanate type, an epoxy type, a melamine type, a silicone type (silane coupling agent) or the like can be used as a crosslinking agent, and any resin can be used without particular limitation as long as it can be crosslinked. Considering not only the cross-linking of the resin but also the adhesiveness to the vapor-deposited thin film made of metal and / or inorganic substance, the silicone type (silane coupling agent)
Can be suitably used.

As described above, not only the adhesion between the fiber and the vapor-deposited thin film is improved, but by coating the vapor-deposited thin film with the resin layer, a vapor-deposited fiber structure having an overall durability can be obtained.

Further, the following manufacturing method is provided in order to exert such an effect.

In the method for producing a vapor-deposited fiber structure according to the present invention, (1) a resin containing a silicone-based resin and a melamine-based resin is applied to the surface of the fiber structure in order to provide the above-mentioned high adhesive strength. Step, (2) oxidizing the surface layer of the silicone resin by plasma treatment, (3) depositing a thin film containing a metal and / or an inorganic substance, (4)
The step of coating with a resin cross-linked product mainly comprises four steps.

That is, in the method of the present invention, a resin film containing a melamine-based resin and a silicone-based resin is first formed on the surface of the fiber structure by coating dipping, and the silicone-based resin is heat-treated to form a silicone. A resin layer is formed, and plasma treatment, more precisely low-temperature plasma treatment, is activated on it to activate the silicone resin (silicon dioxide is uniformly generated on the molecular order by plasma treatment). A predetermined vapor deposition film is formed on the resin film by a vapor deposition process.

The adhesive force between the activated silicone resin film and the vapor-deposited film is greatly improved, and the vapor-deposited thin film is less likely to peel off from the fiber surface. Furthermore, by coating the vapor-deposited thin film with a resin layer, a vapor-deposited fiber structure having excellent wear resistance can be obtained.

In the present invention, as the silicone resin, for example, methylhydrogen polysiloxane emulsion can be used. The content of the silicone resin is preferably about 2 to 10% by weight, and the melamine resin is preferably about 1 to 5% by weight. Melamine resin is
There is a problem that the silicone resin mainly serves as a cross-linking agent and the durability of the silicone resin against washing and friction is reduced when the melamine resin is not used.

As a method of applying the silicone resin to the surface of the fiber cloth, for example, the dipping method can be used, and the drawing ratio is preferably about 20 to 60%.

The conditions of drying and curing after coating are preferably continuous conditions of 160 ° C. for about 2 minutes.

The conditions of the low temperature plasma treatment are, for example, vacuum degree: 20 to 100 Pa, discharge power: 2 to 7K.
V, processing speed: about 5 to 30 m / min is preferable. 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 is preferably changed depending on the chemical composition of the silicone-based resin layer. From the viewpoint of effect, the elemental composition of the silicone-based resin layer is
From the viewpoint of adhesiveness, it is preferable to use 1 or more silicon atoms with respect to 2 carbon atoms.

As a method of coating the resin layer on the vapor-deposited thin film in the present invention, the resin can be applied by a conventional method such as a dipping method, a spray method or a coating method, but the application by the coating method is preferable from the viewpoint of improving abrasion resistance. . The resin layer is preferably cross-linked, and the content of the cross-linking agent varies depending on the resin, but is usually preferably about 1 to 10% by weight based on the resin solid content.

The method for depositing the deposited thin film is not particularly limited. For example, equipment is placed in various thin film forming devices such as a vacuum deposition device, a sputtering device, an ion plating device, and vapor deposition of a desired thickness is performed under reduced pressure. A film may be formed.

In the present invention, in order to coat the resin with the vapor-deposited thin film and coat the vapor-deposited thin film, the resin may be applied and then dried. When a cross-linking agent is used, curing conditions suitable for the cross-linking agent, It may be processed under aging conditions.

In the present invention, the strengthening of the adhesive force between the vapor-deposited thin film and the fiber is achieved by forming an oxidized silicone resin film, and with other resin films,
The desired high adhesive strength cannot be obtained. 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 the plasma treatment, the silicone resin, only when it is also oxidized, has a target high wash resistance. And wear resistance are obtained. Further, only the product coated with the resin layer can obtain higher wear resistance.

The fiber structure of the present invention is an aggregate composed of single fibers (long fibers and short fibers) of synthetic fibers and / or natural fibers, and its form is woven fabric, knitted fabric, non-woven fabric, string,
Examples include belts, ropes and cotton.

The natural fibers referred to here are, for example, cotton, wool,
It refers to silk. Synthetic fibers include, for example, polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polylactic acid, polyamides such as nylon 6 and nylon 66, and acrylic, polyethylene, polypropylene, polyurethane, and the like.
Further, fibers made of their copolymers and blends may be mentioned. From the viewpoint of versatility, it is preferable to use polyester or polyamide as the synthetic fiber. Among them, polyester fibers are more preferable. Further, these may contain additives such as other polymers, matting agents, flame retardants, antistatic agents and pigments, and may be subjected to weight reduction processing from the viewpoint of texture.

Since the present invention is free from the problems of peeling and dropping as in the prior art and is excellent in durability and also has softness, it is developed as a textile product made of a vapor deposition material such as an electromagnetic wave absorbing material and an interference coloring material. The major advantage is that there are no restrictions on the applications.

The fiber structure of the present invention is used as a clothing product.
Since it has excellent durability as well as general clothing, it is suitable for use in uniforms and sports.
Further, as a clothing product, it can be suitably used for gloves, bags, shoes and the like.

Further, it is also suitably used as an interior for curtains, carpets, sheets, wallpapers, etc., amenity and bedding applications, cushions, stuffed animals, etc.

[0037]

EXAMPLES The present invention will be described below with reference to examples.

The test items and conditions in the present invention are as follows.

(1) Washing resistance: JIS-L-1096 L
According to -5 method.

(2) Rubbing resistance: Hold samples at 3 cm intervals,
The surface state after rubbing the vapor deposition surface 100 times was observed.

[0041] ◎: No surface change / deposition by vapor deposition ∘: Almost no surface change, no vapor deposition peeling △: Almost no surface change / Slight vapor deposition peeling ×: Surface change / deposition by vapor deposition (3) Wear resistance: According to JIS-L-0894 II type.

(4) Scratch resistance: JIS-L-0894 II
According to the model, Velcro tape (male, registered trademark) was used instead of the cotton cloth.

⊚: No surface change / deposition by vapor deposition ○: Almost no surface change / deposition by vapor deposition Δ: Almost no surface change / deposition by vapor deposition slightly: X: surface change / deposition by vapor deposition Also, X-ray photoelectrons in this example The analysis conditions for carbon atoms and silicon atoms by spectroscopy 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: leV Vacuum degree: ˜1 × 10 −8 mbar Geometry: θ (escape angle) = 0 ° Further, X-ray Photoelectron spectroscopy refers to X irradiation on the sample surface.
It measures the intensity of photoelectrons that are excited by rays and emitted from the surface as a function of kinetic energy, and then obtains the photoelectron spectrum. It can be used not only for elemental analysis of substances, but also for composition analysis of substances from the beak 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. In addition, the following examples
The processing level of the comparative example is shown in Table 1. Example 1 A polyester filament yarn (40 denier × 18 filaments, a fiber having a substantially circular cross section), which was a tricot knitted fabric (half of knitting structure), was scoured / intermediately set, and then silicone was applied by a dip method at 160 ° C. It was heat-treated to form a silicone resin. After that, low-temperature plasma treatment is applied, and Al on one surface of the knitted film has a film thickness of 80 nm.
Was deposited by the induction heating vacuum deposition method.

After vapor deposition, a material obtained by adding vinylethoxysilane as a crosslinking agent to silicone-modified polyether polyurethane was knife-coated on the vapor-deposited film to form a resin layer.

The silicone resin used was a methylhydrogen polysiloxane emulsion, and a melamine-based one was used as the crosslinking agent.

The processing conditions by the dipping method and the coating method and the plasma processing conditions are as follows.

Dip treatment: Silicone-based resin content: 7% Melamine-based crosslinking agent content: 3% Dip treatment Squeeze ratio: 40% Drying / Cure: 160 ° C. × 2 minutes Plasma treatment: Vacuum degree: 40 Pa Treatment atmosphere: Atmosphere Medium Discharge power: 5.5 KV Treatment speed: 20 m / min Treated surface: Both sides Coating treatment: Solvent-based polyurethane resin: 100 parts Vinyl ethoxysilane: 3 parts Clearance: 0.01 mm Drying / curing: 120 ° C x 2 minutes / 160 ° C X2 minutes As shown in Table 2, the obtained fiber structure had a wash resistance,
It was very strong in rubbing resistance, abrasion resistance, and abrasion resistance. Example 2 A polyester filament yarn (vertical 50 denier × 18 filaments, approximately round cross-section fiber and weft 75 denier × 36 filament, approximately round cross-section fiber) was used as plain weave (vertical 110 / inch, horizontal 81 / inch). A fiber structure was produced in the same manner as in Example 1 except that the scoured and intermediate set fabric was used.

As shown in Table 2, the obtained fiber structure was very strong in washing resistance, kneading resistance, abrasion resistance, and abrasion resistance. [Example 3] Al having a film thickness of 80 nm and SiO 2 on one side of a knitted fabric
Was produced by the same method as in Example 1 except that each metal was laminated and vapor-deposited by the induction heating vacuum vapor-deposition method so that the thickness was 30 nm and Cr was 0.8 nm.

The obtained fibrous structure had an interference coloring property.

As shown in Table 2, the obtained fiber structure was very strong in washing resistance, kneading resistance, abrasion resistance and abrasion resistance. [Example 4] Al having a film thickness of 80 nm and SiO 2 on one side of the woven fabric
Was produced by the same method as in Example 1 except that each metal was laminated and vapor-deposited by the induction heating vacuum vapor-deposition method so that the thickness was 30 nm and Cr was 0.8 nm.

The obtained fiber structure had an interference coloring property.

As shown in Table 2, the obtained fiber structure was very strong in washing resistance, kneading resistance, abrasion resistance and abrasion resistance. [Comparative Example 1] A fiber structure was produced in the same manner as in Example 3 except that plasma treatment was not performed.

As shown in Tables 1 and 2, since the plasma treatment was not performed, the number of carbon atoms: silicon atoms was 2.
It was 0: 0.76, and it was a vapor-deposited fiber structure having good adhesiveness between the silicone resin layer and the vapor-deposited film. [Comparative Example 2] A fiber structure was produced in the same manner as in Example 3 except that the coating treatment using the resin was not performed.

As shown in Table 2, it was a vapor-deposited fiber structure having a rubbing resistance and a scratch resistance because it had no coating layer. [Comparative Example 3] A fiber structure was produced in the same manner as in Example 3 except that the silicone resin was not used.

As shown in Table 2, since the silicone resin was not used, the vapor deposition fiber structure was inferior in overall durability. [Comparative Example 4] A fiber structure was produced in the same manner as in Example 3 except that an acrylic resin was used instead of the silicone resin.

As shown in Table 2, since a resin other than a silicone resin was used, the vapor deposition fiber structure was inferior in overall durability. [Comparative Example 5] The procedure of Example 3 was repeated except that a polyurethane resin was used instead of the silicone resin.

As shown in Table 2, since a resin other than the silicone resin was used, the vapor deposition fiber structure was inferior in overall durability.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

As described above, according to the vapor-deposited fiber structure 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 allows the vapor-deposited film to be formed. It is possible to obtain a fibrous structure having a very high adhesive strength between them and the vapor-deposited film, which is difficult to peel off, and which has excellent washing resistance, kneading resistance, abrasion resistance, and abrasion resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06M 10/02 D06M 15/423 15/423 15/643 15/643 11/00 C F term (reference) 4F100 AA01A AB01A AK01D AK36B AK41C AK52B AL06B BA04 BA07 BA10C BA10D CA02D DG00C EH462 EH66A EH662 EJ05D EJ122 EJ61B EJ612 4K029 AA11 AA23 BA03 BA07 BA46 BB02 BC02 BD00 CA01 FA05 FA07 4L031 AA18 AB04 CB05 DA00 DA20 4L033 AA01 AA06 AB04 AB09 AC08 BA57 BA96 CA24 CA59

Claims (6)

[Claims] 1. A fiber structure in which a vapor-deposited thin film containing a metal and / or an inorganic substance is laminated on at least a part of the fiber surface, and the vapor-deposited thin film is an intermediate product containing at least an oxidized silicone resin and melamine resin. A vapor-deposited fiber structure, which is laminated on a fiber structure via an agent and in which the vapor-deposited thin film is covered with a resin layer. 2. The vapor-deposited fiber structure according to claim 1, wherein the oxidized silicone-based resin is produced by plasma treatment. 3. The vapor-deposited fiber structure according to claim 1, wherein the elemental composition of the intermediate agent is such that, in the vicinity of the vapor-deposited thin film, 1 carbon atom is 2 or more silicon atoms. 4. The vapor-deposited fiber structure according to any one of claims 1 to 3, wherein the resin layer is cross-linked with a cross-linking agent containing a silane coupling agent as a main component. 5. The fiber material constituting the fiber structure is mainly polyester fiber.
5. The vapor-deposited fiber structure according to any one of 4 to 4. 6. A step of applying a resin containing a silicone resin and a melamine resin to the surface of a fiber structure, a step of oxidizing the surface layer of the silicone resin by plasma treatment, and a thin film containing a metal and / or an inorganic material deposited by vapor deposition. And a step of coating with a resin, the method for producing a vapor-deposited fiber structure.