JP3712310B2 - Polymer molding having antibacterial properties - Google Patents

Description

【００２１】
実施例５
実施例１において、高分子成形物としてアクリロニトリル重合体からなるフィルムを用いた以外は同様にして実験を行なった。この場合にも、得られたフィルムは良好な抗菌性を示した。
【００２２】
【発明の効果】
本発明の抗菌性高分子成形物は、抗菌性にすぐれるとともに、その抗菌作用は耐久性の良いものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymer molded article having antibacterial properties.
[0002]
[Prior art]
As a method for producing antibacterial fibers, a method of spinning by adding a zeolite carrying an antibacterial organic compound or an antibacterial metal to a dope is often used. In addition, the present inventors have proposed a method for introducing a carboxyl group into an acrylic fiber, and proposed an antibacterial fiber by substituting a metal for the carboxyl group (Japanese Patent Laid-Open No. 7-238469). There is also a method of attaching various antibacterial agents to the fiber surface using a binder. Neither of them is satisfactory yet, including the problem of cost and the persistence of antibacterial action.
Recently, manufacturers of synthetic fibers tend to dislike spinning many types of fibers from the standpoint of profitability, and it is considered that various functions should be added after spinning. The same applies to antibacterial fibers.
In addition, there is a strong demand for antibacterial films and containers, but so far there is almost nothing that can be satisfied.
[0003]
[Problems to be solved by the invention]
This invention makes it the subject to provide the antibacterial polymer molding which can be manufactured by carrying out surface processing with respect to the polymer molding after shaping | molding.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, according to the present invention, in a molded product in which at least a surface portion is formed of a polymer material containing a cyano group and / or a thiocyano group, the surface is monovalent via the cyano group and / or thiocyano group. An antibacterial property characterized by supporting copper ions, wherein the chloride ion content and nitrate ion content in the cyano group and / or thiocyano group-containing polymer material is 400 wtppm or less in total. Is provided.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the polymer molded product of the present invention, at least the surface portion is formed of a polymer material containing a cyano group (—CN) and / or a thiocyano group (—SCN).
Such materials include various conventionally known materials such as fibers (yarns), woven fabrics, non-woven fabrics, knitted fabrics, films, plates, rods, containers, and other articles.
The polymer molded product in the present invention does not necessarily need to be entirely composed of a polymer material having a cyano group and / or a thiocyano group, and only the surface portion of the molded product is formed from such a polymer material. It may be a thing. As a formed product made of a polymer material having a cyano group and / or a thiocyano group only on the surface portion, a film made of a polymer material containing a cyano group and / or a thiocyano group may be a film made of another polymer material, or other moldings. Examples thereof include those obtained by laminating and adhering to a product, and those obtained by applying a solution of a polymer material containing a cyano group and / or a thiocyano group to a surface of a molded product made of another polymer material and drying.
[0006]
Examples of the polymer material containing a cyano group include acrylonitrile polymers and acrylonitrile copolymers. A polymer material containing a thiocyano group can be obtained by reacting potassium thiocyanate with a polymer material containing a halogen such as chlorine.
In the polymer material containing a cyano group and / or thiocyano group, the content of the cyano group and / or thiocyano group is 100 to 500 g, preferably 170 to 490 g, in 1000 g of the polymer material.
A preferable polymer molded product used in the present invention is an acrylic fiber. The acrylic fiber includes acrylic fiber and modacrylic fiber.
Another preferred polymer molding used in the present invention is a film or a container. The film or container can be formed using an acrylonitrile polymer or copolymer or a blend of these with other polymers.
[0007]
In order to produce the polymer molded product having antibacterial properties of the present invention, the molded product is brought into contact with an aqueous solution containing a divalent copper ion and a reducing agent capable of reducing the divalent copper ion to a monovalent copper ion. Thereby, monovalent copper ions are supported on the surface of the molded product via the cyano group and / or thiocyano group. In this case, it is necessary to control the concentration of chlorine ions and nitrate ions contained in the aqueous solution, and the concentration in the aqueous solution is 0.03 wt% or less, preferably 0.01 wt% in the total amount thereof. Hold below. When these chlorine ions and nitrate ions are mixed in a molded product containing monovalent copper ions as a product, the monovalent copper ions are changed into divalent copper ions and metallic copper, and the copper is retained in the molded product. Since it disappears, it is not preferable.
[0008]
Examples of the divalent copper ion source include divalent copper compounds such as copper sulfate, copper acetate, copper citrate, and copper hydroxide. In the present invention, it is not preferable to use copper chloride or copper nitrate as the divalent copper ion source. The amount of the divalent copper compound added to the aqueous solution is 0.005 to 0.1 mol, preferably 0.01 to 0.05 mol, per liter of the aqueous solution.
Any reducing agent can be used as long as it can reduce divalent copper ions to monovalent copper ions in an aqueous solution. For example, hydroxylamine, ferrous sulfate, sulfite waste liquor, vanadic acid Ammon, furfural, ascorbic acid, metallic copper and the like can be mentioned, and the use of metallic copper is particularly preferable. The amount of these reducing agents used is 1 to 10 moles, preferably 1 to 3 moles per mole of the divalent copper compound.
The contact temperature between the aqueous solution containing the divalent copper compound and its reducing agent and the molded product is 70 to 110 ° C, preferably 80 to 105 ° C. The contact time is 30 minutes or longer, usually 60 to 120 minutes.
[0009]
In the aqueous solution used in the present invention, an organic compound having a sulfonic acid group, such as a surfactant having a sulfonic acid group, is used in order to increase the stability of the monovalent copper ion generated by reduction of the divalent copper ion. It is preferable to add an acid dye or the like. The concentration of the sulfonic acid group-containing organic compound in the aqueous solution is 0.005 to 5 wt%, preferably 0.01 to 2 wt%.
[0010]
The polymer molded article having antibacterial properties according to the present invention contains monovalent copper ions on its surface via its cyano group and / or thiocyano group. The content of the monovalent copper ions is about 0.02 to 0.2 g, preferably about 0.03 to 0.15 g per m ² as metallic copper exposed on the surface. Further, in the polymer molded product of the present invention, the chloride ion content and the nitrate ion content are 400 wtppm or less, preferably 100 wtppm or less, as a total amount thereof. When the chloride ion content and the nitrate ion content exceed the above ranges, the monovalent copper ions supported on the molded product are converted to metallic copper and divalent copper ions over time, and the molded product has antibacterial properties. Will disappear. The chloride ion content and the nitrate ion content contained in the polymer molded product are regulated to a specific amount or less by controlling the chlorine ion concentration and nitrate ion concentration in the aqueous solution used as the treating agent for the polymer molded product. be able to.
In the polymer molded article having antibacterial properties according to the present invention, the antibacterial action is very excellent in water resistance and durability, and even when it comes into contact with water, acid or alkali, it easily disappears. There is nothing to do.
[0011]
Next, the present invention will be described in more detail with reference to examples. In the following, “%” is the percentage of the fiber weight unless otherwise specified.
[0012]
Example 1
Silpalon 100 / -40 (acrylic filament yarn manufactured by Mitsubishi Rayon Co., Ltd.), sulfuric acid (50 ° Be) 3%, copper sulfate (II) 5%, copper net (diameter 0.28 mm, 15 mesh) 30%, Emar 10 (Sulphonic acid group-containing anionic surfactant) Immerse in a 10% aqueous solution at a bath ratio of 1:15, gradually heat up, heat-treat at 103 ° C. for 60 minutes, and then wash thoroughly with water. The resulting fiber showed a 5.2% weight gain and, as a result of the analysis, contained 1.03% monovalent copper ions.
In addition, the chlorine ion and nitrate ion contained in the aqueous solution were not detected by a usual analysis method, and the total content of chlorine ion and nitrate ion in the product fiber was substantially zero%.
[0013]
Example 2
The experiment was conducted in the same manner as in Example 1 except that 1% of a sulfonic acid group-containing acid dye (CI Acid Green 25) was used instead of Emar 10. The resulting fiber showed a 0.93% weight gain and, as a result of the analysis, contained 0.40% monovalent copper ions.
[0014]
Example 3
Silparone 100 / -40 was immersed in an aqueous solution containing 3% sulfuric acid, 5% copper sulfate and 30% copper mesh at a bath ratio of 1:15, gradually heated, and heat-treated at 103 ° C. for 60 minutes. Wash with water. The resulting fiber showed a 0.55% weight gain due to copper ion adhesion.
In addition, the chlorine ion and nitrate ion contained in the aqueous solution were not detected by a usual analysis method, and the total content of chlorine ion and nitrate ion in the product fiber was substantially zero%.
[0015]
Example 4
Cashmere 1 FCW 7d × VC (acrylic staple manufactured by Asahi Kasei Kogyo Co., Ltd.) in an aqueous solution containing 3% sulfuric acid, 5% copper sulfate, 30% copper mesh and 1% sulfonic acid group-containing acid dye (CI Acid Green 25) : Immerse at 15, gradually raise the temperature, heat-treat at 100 ° C. for 60 minutes, and then wash thoroughly with water. The resulting fiber showed an increase of 1.99%.
[0016]
Example 5
Protex 2d x 51 mm (acrylic fiber manufactured by Kaneka Chemical Industry Co., Ltd.) is immersed in a 2% aqueous solution of 3% sulfuric acid, 5% copper sulfate, 15% copper mesh, and 10% Emar at a bath ratio of 1: 7 and gradually. The mixture is heated to 100 ° C., heat-treated at 100 ° C. for 60 minutes, and thoroughly washed with water. The resulting fiber showed an increase of 2.12%.
[0017]
Comparative Example 1
The experiment was performed in the same manner as in Example 1 except that 1 wt% of sodium chloride was added in excess.
[0018]
Comparative Example 2
The experiment was performed in the same manner as in Example 1 except that 2 wt% of sodium nitrate was added.
[0019]
Next, the fibers obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were tested for antibacterial properties, acid resistance, and alkali resistance as described below, and further, changes in properties over time were examined. The results are shown in Table 1.
(1) Antibacterial test test method: Processing evaluation test manual of antibacterial and deodorant processed product, shake flask method test bacterium: Klebsiella pneumoniae, Klebsiella pneumoniae ATCC 4352
Shaking conditions: List action 330 rpm x 1 hour Washing method: 10 times according to the method according to JIS L 103 method (2) Acid resistance test Judgment by elution amount after immersion for 1 hour at room temperature in sulfuric acid 15 w / v% ( (Bath ratio 1: 100)
(3) Alkali resistance test A solution with a pH of 12 is prepared with sodium hydroxide, and determined by the amount of elution after immersion for 1 hour at room temperature (bath ratio 1: 100).
(4) Change in properties over time Leave in a room at 60 ° C. and 98% relative humidity for 65 days.
[0020]
[Table 1]

[0021]
Example 5
In Example 1, an experiment was conducted in the same manner except that a film made of an acrylonitrile polymer was used as the polymer molding. Also in this case, the obtained film showed good antibacterial properties.
[0022]
【The invention's effect】
The antibacterial polymer molded product of the present invention is excellent in antibacterial properties, and its antibacterial action has good durability.

Claims (3)

In a molded article in which at least the surface portion is formed of a polymer material containing a cyano group and / or a thiocyano group, a monovalent copper ion is supported on the surface via the cyano group and / or thiocyano group. A polymer molded article having antibacterial properties, wherein the total content of chloride ion content and nitrate ion content in the cyano group and / or thiocyano group-containing polymer material is 400 wtppm or less. The polymer molded product according to claim 1, wherein the polymer molded product is an acrylic fiber. The polymer molded article according to claim 1, wherein the polymer molded article is a film or a container.