JP2588250B2 - Composite fabric containing copper ions and / or silver ions - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a composite fabric having antibacterial properties and moisture permeability.

[Conventional technology]

A composite fabric formed by laminating or impregnating a resin film having moisture permeability on a fiber base cloth is ski wear,
It is used as a moisture-permeable waterproof clothing such as jogging wear, parka, kappa, and diaper cover. Even if this moisture-permeable waterproof clothing has moisture permeability, sweat and secretions remain between the clothing and the skin surface when the amount of perspiration is greater than the moisture permeability,
Bacteria that propagate there may cause body odor to cause discomfort, or bacterial infection may cause skin irritation.

For this reason, various attempts have recently been made to provide clothing having antibacterial properties.

That is, it has been known that metals such as copper and silver have an antibacterial effect, and by utilizing this property, a method of twisting a copper wire with a yarn such as a fiber product (Japanese Patent Laid-Open No. 52-127899).
Japanese Patent Application Laid-Open No. 54-160900), a method of applying a resin containing fine powder of a water-insoluble copper compound or a silver compound to a fiber surface (Japanese Patent Application Laid-Open No. 54-160900). JP-A-62-53348) has been proposed.

[Problems to be solved by the invention]

However, among the above-mentioned conventionally known methods, sweat during wearing, rust of copper wire due to washing, copper compound peels off due to abrasion, etc., dissolution of metal is insufficient and sufficient antibacterial property cannot be obtained, etc. And it was difficult to obtain a satisfactory antibacterial garment.

The present invention has been made in view of the above-mentioned drawbacks, and as a result of intensive studies, it has been proposed to provide a composite fabric material exhibiting stable antibacterial properties in long-term wear.

[Means for solving the problem]

That is, the present invention is a resin having a moisture permeability ^{500g / m 2 / 24hr (JIS} L-1090 A method) or the composite fabric-like material in which the resin film is formed by laminating or impregnating with a moisture permeability fiber base fabric It is a composite cloth-like material in which particles obtained by blending a compound capable of eluting copper ions and / or silver ions into a film into a soluble glass are dispersed in a film.

In the present invention, the compound capable of eluting copper ions and / or silver ions may be any compound that becomes a metal ion or a metal ion-forming product (a substance that easily becomes a metal ion) in or after elution from glass. Specifically, as the copper compound, Cu ₂ O, Cu ₂ S, CuO, CuS, copper halide, Cu
Inorganic compounds such as (OH) ₂ and CuSO _4, and organic compounds such as copper acetate, copper aminoacetate, and copper formate can be used.
As the silver compound, an inorganic compound such as Ag ₂ O, Ag ₂ S, AgNO ₃ , silver halide, Ag ₂ SO ₄ , Ag ₂ CO ₃ , or an organic compound such as silver acetate, silver oxalate, or silver salicylate is used. be able to.

From the viewpoint of compatibility with the melting glass and the metal content, Cu
O, CuO ₂ or Ag ₂ O is preferred.

The melting glass of the present invention is a particle size of 500 μm pass 350 μm
The remaining glass particles (1 g) were put into distilled water (500 ml), and expressed at a glass particle diameter reduction rate (μm / hr) in air bubble stirring at 40 ° C., of 0.001 to 100 μm / hr, preferably 0.005 to 60 μm / h.
r. If the reduction rate is less than 0.001, satisfactory antibacterial performance cannot be obtained. When the decreasing rate is 100 μm / hr, stable antibacterial performance over a long period cannot be obtained.

The melting glass of the present invention is specifically SiO ₂ , B ₂ O ₃ , a network-forming oxide such as P ₂ O ₅ and Na ₂ O, K ₂ O, CaO, MgO, BaO, Al ₂ O ₃ , Z
It is composed of a network modifying oxide such as nO, TiO _{2 and the} like, and its solubility can be adjusted by the composition ratio of these oxides.

The method for producing a soluble glass containing a copper compound or a silver compound is to disperse in a molten glass or to make a gel with a copper compound, a silver compound and a glass component, and 750 to 120.
There is a gel sol method in which firing is performed at a temperature of 0 ° C. The gel sol method is preferred because the melting method does not have good dispersibility.

A copper compound or a silver compound is dispersed in a dissolvable glass, and fine particles can be formed by an ordinary method. The particle size may be such that the mechanical properties of the resin film are not impaired, and is 20 μm or less, preferably 10 μm or less.

The content of the copper compound in the melting glass is preferably 10 to 50% by weight, and the content of the silver compound is preferably 0.5 to 20% by weight.

The amount of metal ions contained in the resin film is 0.01-10% by weight for copper ions and 0.0001-
0.5% by weight.

The resin that can be used for the composite fabric-like material of the present invention can be used for any resin as long as it has moisture permeability.
Polyurethane resin, acrylic resin, silicone resin, polyvinyl alcohol resin, nylon resin, polyester resin, polycarbonate resin, fluorine resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, acrylonitrile Butadiene-
Styrene resins, melamine resins, urea-formalin resins, glyoxal resins, and the like.

To impart moisture permeability to the resin film, a method of foaming the resin film using a foaming agent, a method of adding and extracting fine particles to the resin film, and freely mixing the solvent in the resin solution with the solvent in a non-solvent of the resin A porous resin film having a pore diameter of 1 mm or less and a porosity of 20% or more is manufactured by a method such as extraction with a solvent which does not form a pore, or -SO ₃ H, -SO ₃ M (M: alkali metal or _{-NH 4), - COOM, -COOH} , -NH 2, -CN, -OH, -NHCON
A method for introducing a hydrophilic group such as H _2.

The resin film of the present invention may contain various additives commonly used for resins. For example, heat stabilizers, antioxidants, light stabilizers, leveling agents, water repellents, curing agents, plasticizers, thickeners, pigments, gloss-imparting agents, flame retardants, and the like.

The material that is the fiber base fabric of the present invention may be any of synthetic fibers and natural fibers, and any structure such as woven fabric, knitted fabric, and nonwoven fabric can be used.

To form a resin film on a fiber base fabric by lamination or impregnation, a method of applying a resin solution in which a resin is dissolved in a solvent to the fiber base fabric, or a method of melting the resin and applying it to the fiber base fabric, There is also a method of impregnating a fiber base cloth with a resin solution in which a resin is dissolved or dispersed in a solvent.

In order to obtain a stable composite fabric, water repellency and calendering can be performed as a pre-treatment before forming the resin film. And flame-retardant processing.

The antibacterial property of the composite fabric of the present invention is based on Trichophytonment belonging to Trichophyton.
agrophytee, IFO 5466), Trichophyton Labram (T
richophyton rubrum, IFO 5467), Aspergillus flavus, IFO 6343, Aspergillus niger, IFO 6341, Penicillium citrium, IFO 635
2), Fusalium Lini (IFO 4468),
Rhizopus nigricans (IFO 578)
1), Cladosporium resini
nae, IFO 8588), Pseudomonas bacteria,
Shows strong bactericidal action against Staphylococcus aureus and Escherichia coli. It also shows excellent mold resistance to molds other than bacteria.

In the present invention, a compound in which a copper ion or a silver ion elutes or a compound forming an ion is dispersed in a soluble glass is dispersed in a resin film.

Therefore, copper ions and silver ions can be stably supplied from the melting glass for a long period of time. In addition, it is considered that since it has an appropriate moisture permeability, ions are appropriately eluted together with the permeation of water vapor and stably exhibit antibacterial performance for a long time. As described above, according to the present invention, the antibacterial property can be maintained stably for a long period of time by the synergistic effect of the melting glass and the moisture permeability of the resin film.

(Example) The measuring method of the characteristic shown in the example is as follows.

(Antibacterial property) (1) Bacteria used Staphylococcus aureus FDA 209P (2) Test method Halo-test method according to AATCC TEST METHOD 90 (moisture permeability) Measured by JIS L-1099A method. The unit was converted to g / m ² / 24hr (washability) In order to check the durability of antibacterial performance, it was carried out according to the JIS-0217-103 method.

Example 1 36 parts by weight of B ₂ O ₃ , SiO _{2 based on} 20 parts of a polyurethane elastomer comprising isophorone diisocyanate, polyethylene glycol (molecular weight: 2,000) and 1,4 butanediol
_A resin solution composed of 2 parts of a soluble glass (particle size: micron) composed of 217% by weight, 5% by weight of Na ₂ O and 42% by weight of CuO, 48 parts of dimethylformamide and 30 parts of methyl ethyl ketone was prepared.

Apply this resin solution to the fiber base cloth (70 denier nylon 66 plain weave density 136 / in) with a knife over roll coater.
Apply to a weft density of 104 / in) and use a pin tenter
Heat treatment was performed at 100 ° C. for 3 minutes.

The resin application amount of the composite fabric obtained by the above processing is 30.
g / m ² .

Comparative Example 1 Two parts of the soluble glass used in Example 1 were 100 parts of a Saran resin (KSO-1 manufactured by Asahi Kasei Kogyo Co., Ltd.) and 2 parts of a thickener (Pramile ASE-60 manufactured by Nippon Acrylic Chemicals, Inc.). And Cu was prepared so as to be 5% by weight with respect to the Saran polymer. Using this resin solution, a composite fabric was produced in the same manner as in Example 1.

Example 2 95 parts of low density polyethylene having a specific gravity of 0.92, a nucleating agent (0.5 parts of sodium bicarbonate, 0.5 parts of citric acid), 29% by weight of B ₂ O ₃ ,
iO ₂ 51% by weight, Na ₂ O 10% by weight, ZnO 4% by weight, Al ₂ O ₃ 1
Wt%, 5 wt% Ag ₂ O melting glass (particle size 3
Micron) 4 parts were blended, heated and melted, then foamed polyethylene film (thickness 100 microns, pore size 2) by T-die method
A porosity of 50 microns (80%) was obtained.

Next, the expanded polyethylene film and the fiber base cloth (75
85 parts of polyurethane adhesive (Chrisbon 4160LV manufactured by Dai Nippon Ink Co., Ltd.), 10 parts of cross-linking agent (Bernoff DN 950 manufactured by Dai Nippon Ink Co., Ltd.), 10 parts of cross-linking agent (Chris Bon Accel) T) An adhesive solution containing 5 parts was applied on a film in a dot-like manner (20 points / cm ² ), and then a fiber base fabric was joined and hot-pressed at 100 ° C. at 3 kg / cm ^{2 to} form a composite fabric. The coating amount of the obtained adhesive was 1 g / m ² .

Comparative Example 2 In the production of the film of Example 2, a non-porous polyethylene film without a nucleating agent (thickness: 50 microns)
I got Next, a composite fabric was produced from this film in the same manner as in Example 2.

Example 3 Polyvinyl alcohol resin (Nippon Synthetic Chemical Industry Co., Ltd.)
10 parts of Gohsenol NL-05), 3 parts of melamine resin (Sumitex Resin M-3, Sumitomo Chemical Co., Ltd.),
Organic amine (Sumitomo Chemical Co., Ltd., Sumitex Accelerator ACX) 0.5 part, water 86 parts, B ₂ O ₃ 15% by weight, SiO ₂ 55% by weight, Na ₂ O 10 parts by weight, Ag ₂ O 20 parts by weight of soluble glass (glass particle diameter reduction rate 0.025
(μm / hr, particle size: 1 micron) was prepared from a resin solution consisting of 0.5 part.

After immersing a fiber base cloth (75 denier polyester twill with a density of 129 yarns / in and a weft density of 86 yarns / in) in this resin solution, squeezing it with a rubber roll to a squeezing rate of 60%, and using a pin tenter at 150 ° C for 2 minutes Heat treatment was performed to produce a composite fabric.

Comparative Example 3 70% by weight of B ₂ O ₃ and SiO ₂ 15 based on the polyvinyl alcohol resin, the melamine resin, and the organic amine used in Example 3.
Wt%, Na ₂ O 10 wt%, Al ₂ O ₃ 4% by weight, Ag ₂ O 1% by weight
Melting glass consisting of (glass particle diameter reduction rate 150μm / h
r, particle size 1 micron) and a resin solution consisting of 10 parts of water and 76.5 parts of water.

This resin solution was used to produce a composite fabric using the same fiber base fabric and processing method as in Example 3.

Table 1 shows the results of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3. The composite fabric of the present invention exhibits stable antibacterial performance for a long period of time.

[Effect of the Invention] The composite fabric-like material of the present invention has excellent antibacterial properties, and furthermore, has a long-term stable antibacterial property by appropriately eluting copper ions and / or silver ions by the moisture permeability function of the resin film. Demonstrate performance.

As a result, the composite fabric material having antibacterial performance can be applied to general clothing including waterproof clothing such as ski wear, jogging wear, hoodies, kappa, and diaper covers, and can be widely used.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location D06M 23/08 D06M 11/12

Claims (1)

(57) [Claims] 1. A composite fabric-like material in which the resin film is formed by laminating or impregnating with a moisture permeability fiber base fabric, moisture permeability 500 g / m ^2/24 hr or in more resin film copper ions and / A composite fabric-like material characterized by dispersing particles obtained by blending a compound capable of eluting silver ions into a soluble glass.