JPH0343456A - Antibacterial resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having a durable antibacterial activity and suitable for preparing fiber products such as waddings or hosieries, packaging films, etc., and having a specific average particle size by compounding a resin with a specific amount of water-containing metal oxide particles carrying a specified amount of metal ions. CONSTITUTION:A resin (e.g. a polyamide or polyethylene terephthalate) is compounded with 0.01-20wt.%, preferably 0.1-10wt.%, of water-containing metal oxide particles carrying 0.1-20wt.%, preferably 0.5-12wt.%, of the ions of one kind or more selected from silver, copper, zinc, gold and platinum, and having an average particle size of <=10 mum, preferably <=3 mum, and a specific surface area of >=3m<2>/g to provide the objective resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an antibacterial resin composition, and more particularly to an antibacterial resin composition containing hydrated metal oxide particles having an antibacterial effect.

[Conventional technology] Synthetic fibers such as polyester, nylon, and acrylic are
Due to its excellent properties such as heat resistance and chemical resistance, it is suitable for clothing,
It is widely used for industrial materials, bedding, etc.

In recent years, there has been an increasing demand for fibers with antibacterial properties as one of the comfort functions in these fiber applications.

Generally, methods for imparting antibacterial properties to fibers include attaching aromatic halogen compounds, organosilicon-based quaternary ammonium salts, organic nitrogen compounds, etc. to the fibers, but these compounds can be removed by washing, etc. There was a problem with durability because it easily fell off. Therefore, a resin containing zeolite particles with a 3i02/Alz03 molar ratio of 14 or less and a specific surface area of 150 m2/1 or more supporting silver, copper, and zinc ions as an antibacterial agent (Japanese Patent Publication No. 63-5401)
3@Publication> has been proposed. This resin has excellent antibacterial properties and durability. However, since these particles easily absorb moisture, they may foam when blended into resin.
Even after being blended into a resin, the particles tend to absorb moisture, resulting in poor moldability and coloring of the resin over time. Therefore, there is a method of improving the moldability of resin by coating zeolite particles with liquid paraffin, a wrinkle-containing coating agent, or a fluorine-based resin to make them hydrophobic (Japanese Patent Application Laid-open No. 7746/1983).
JP-A-62-7747, JP-A-62-7748) and a method of blending zeolite particles holding metal ions and ammonium ions with a discoloration inhibitor (JP-A-62-7748).
-265958) has been proposed. However, these improvement effects were not sufficient.

[Problems to be Solved by the Invention] The present inventors conducted studies with the aim of providing a resin composition that does not have the drawbacks of the conventional methods described above, has a durable antibacterial effect, and has an excellent antibacterial effect. As a result of our research, we found that the problem could be solved by making hydrated metal oxide particles with an average particle size within a specific range hold metal ions that have antibacterial properties, and by blending a specific amount of hydrated metal oxide particles into the resin. It is.

[Means for Solving the Problems] The object of the present invention described above is to provide at least one metal ion selected from silver, copper, zinc, gold, and platinum in an amount of 0.1 to 2
This can be achieved by using a resin composition having antibacterial properties, which contains 0.01 to 2Q% by weight of hydrated metal oxide particles having an average particle diameter of 10 μm or less, which are supported at 0% by weight and 1% by weight. can.

The average particle diameter of the hydrous metal oxide particles used in the present invention must be 10 μm or less, preferably 5 μm or less, and more preferably 3 μm or less. When the average particle diameter of the hydrated metal oxide particles exceeds 10 μm, the dispersibility of the hydrated metal oxide particles in the resin to which they are added and blended is insufficient, and the moldability of the resulting resin decreases.

The specific surface area of the hydrous metal oxide particles is 3Tr12/g
or more is preferable, and 10 m2/9 or more is more preferable. If the specific surface area is less than 3 m2/9, the amount of metal ions carried by the hydrous metal oxide particles decreases, and the resulting resin tends to have an insufficient antibacterial effect, which is not preferable.

The hydrous metal oxide particles contain at least one metal ion selected from silver, copper, zinc, gold, and platinum in an amount of 0.1 to 2
It is necessary to carry 0% by weight, preferably 0.3 to 15% by weight, and more preferably 0.5 to 12% by weight. If the supported amount of metal ions is less than 0.1% by weight, the antibacterial effect of the obtained resin will be insufficient, and if it exceeds 20% by weight, the antibacterial effect of the obtained resin will be saturated, which is not economical.

The method for supporting metal ions on hydrous metal oxide particles is a simple method in which the metal ions can be supported by conventionally known methods such as ion exchange method and coprecipitation method. The exchange method is preferred.

Furthermore, in addition to the specific metal ions mentioned above, other ions such as ammonium ions can be supported on the hydrous metal oxide particles depending on the purpose.

Specific examples of the hydrous metal oxide particles include antimony r11 (Sb203, 0 day 20), niobium rR (Nb2
05.0 mouth 20), tantalic acid (Ta205.0 day 20)
), bismuth rM (B 1203・0 days 20), titanic acid (TiO2・0 days 20), zirconium acid (Zro
2.0 day 20), iron M (Fe203 ・0 day 20),
stannic acid (SrlOz I rll-f20), zinc M
(ZnO2/0 days 20) and hydrated composite metal oxides containing at least one hydrated metal oxide as a main component selected from these hydrated metal oxide particles. Among these, antimonic acid, titanic acid, niobic acid,
Zirconic acid and its hydrated composite metal oxide are preferred because they have a high ability to support the metal ions mentioned above. Furthermore, it is preferable that these hydrated metal oxides be of non-standard quality since they have a greater ability to support metal ions.

The resin composition having antibacterial properties according to the present invention must have an average particle diameter within the above-described specific range and contain 0.01 to 20% by weight of hydrated metal oxide particles supporting metal ions. It is preferably 0.05 to 15% by weight, and 0.05 to 15% by weight.
More preferably 1 to 10% by weight. If the content of hydrated metal oxide particles is less than 0.01% by weight, the antibacterial effect aimed at by the present invention will be insufficient, and if the content exceeds 20% by weight, the antibacterial effect will be saturated and not only will it become uneconomical. , moldability decreases. The resin may contain two or more types of hydrated metal oxide particles supporting different ion species and/or two or more types of hydrated metal oxide particles having different ion loadings.

There are no particular restrictions on the resin for blending the hydrous metal oxide particles, but specifically, polyamides such as nylon 6 and nylon 66, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polyethylene and polypropylene, Examples include synthetic resins such as polyvinyl alcohol, acrylic resin, and urethane resin. If the resin is hydrophilic, the antibacterial effect of the resulting resin will be greater, so in the case of hydrophobic resins, it is recommended to copolymerize with a copolymer component having a hydrophilic functional group or blend with a hydrophilic resin. is preferred.

In the present invention, the hydrated metal oxide particles can be blended into the resin at any stage.

When melt-mixing the hydrated metal oxide particles with the resin, the hydrated metal oxide particles are added in advance to a concentration of, for example, 120 to 30
Preferably, the components are activated by dehydration at a humidity of 0''G before mixing.

The resin composition of the present invention has cooling properties such as matting agents, deodorants, colorants, ultraviolet absorbers, infrared absorbers, flame retardants, fluorescent brighteners, other ionic adsorbents, and other antibacterial agents. An O agent may be included depending on the purpose.

The resin composition of the present invention has not only antibacterial properties, but also odor resistance and freshness retention properties, so it can be used for textiles such as futon cotton and socks, for films such as packaging films, and for other molded products. Can be used for any purpose. When used in textile applications, it can be used as a composite fiber such as a core-sheath type composite used in the core or sheath, and may be mixed, blended, interwoven, or interwoven.

[Example] The present invention will be described in detail by giving examples below. Each characteristic value in the examples was determined according to the following method.

(8) Average particle diameter of particles: It was determined by electron spectroscopy of the particles.

(8) Amount of metal ions supported on particles: Quantification was done by atomic absorption spectrometry.

(C) Antibacterial evaluation of tube knitted fabric: Test bacteria (E. coli ESCheriChiac
oil NIHJ Staphylococcus aureus 5taphy
l.

C0CCtlS aeretls IFO12732)
of suspension buffer, and in a closed container at 150 times/min, 1
The number of viable bacteria was measured after shaking for a period of time, and the reduction rate relative to the number of bacteria in the outgoing suspension was determined (shake flask method).

Example 1 100 parts by weight of andimonic acid particles were added to 400 parts by weight of a 0.05 mol/Q silver nitrate aqueous solution, and the mixture was stirred at room temperature for 2 hours. , the particles separated by centrifugation were placed on filter paper for 50 minutes.
By slowly adding 0.00 parts by weight of deionized water, the metal ions physically adsorbed on the particle surface were completely washed away.

The obtained particles were vacuum-dried at 150'C for 15 hours to obtain antimonic acid particles (average particle size: 0.9 μm) carrying 2.1% by weight of silver ions. When 30 parts by weight of these particles were mixed with 970 parts by weight of nylon 6 using an extruder, a nylon 6 pellet containing 3.0 parts by weight of antimonic acid particles could be obtained without foaming.

By spinning this pellet using a normal melt spinning method and then drawing it, a drawn yarn of 75 denier and 24 filaments could be obtained without yarn breakage.

This drawn yarn is cylindrically knitted and refined.
Antibacterial properties were evaluated for items that had been washed 0 times.

The bacterial count reduction rate was 99.9 for E. coli in the sample after scouring.
%, 96.6% against Staphylococcus aureus, 98.8% against E. coli after washing, and 92.8% against Staphylococcus aureus, showing excellent antibacterial effects for all samples. It was found that it has.

Examples 2 to 4, Comparative Examples 1 to 3 Using various hydrated metal oxide particles, the same operations as in Example 1 were performed to create hydrated metal oxide particles having different silver ion supported amounts and average particle diameters, This was blended with nylon 6. Next, a drawn yarn was prepared in the same manner as in Example 1, and the yarn was knitted into a tube to evaluate its antibacterial properties. Table 1 shows the evaluation results of moldability and antibacterial properties of the resin.

(Left below) Example 5 Andimonic acid particles 3 carrying silver ions obtained in Example 1
0 parts by weight and 970 parts by weight of modified polyethylene terephthalate (polyethylene terephthalate with a number average molecular weight of 18,000 obtained by copolymerizing 5-sodium sulfoisophthalate @ component at 5 mol% with respect to the total dicarboxylic acid components) using an extruder. It was possible to produce 1 q of modified polyethylene terephthalate pellets containing 3.0 weight percent of antimonic acid particles without causing foaming.

By spinning this pellet using a normal melt spinning method and then drawing it, a drawn system of 24 filaments of 75 denier could be obtained without yarn breakage.

This drawn yarn is cylindrically knitted and refined.
Antibacterial properties were evaluated for items that had been washed 0 times.

The bacterial count reduction rate was 99.9 for E. coli in the sample after purification.
%, 942% against Staphylococcus aureus, 97.1% against Escherichia coli in the sample after washing, and 92.8% against Staphylococcus aureus, all samples have excellent antibacterial effects. I found out that

Example 6 A portion of antimony powder particles washed 100 times was added to 400 parts by weight of an aqueous solution of zinc chloride at a concentration of 0.05 mol/day, and stirred at room temperature for 3 hours. Particles separated by centrifugation were placed on filter paper for 5 minutes.
By slowly adding 1,000 parts by weight of deionized water, the metal ions physically adsorbed on the particle surface were completely washed away. The obtained particles were vacuum-dried at 150'C for 15 hours to obtain antimonic acid particles (average particle size 0.9 μm) carrying 1.3% by weight of zinc ions. When 30 parts by weight of these particles were mixed with 970 parts by weight of nylon 6 using an extruder, nylon 6 pellets containing 3.0 weight 1% of antimonic acid particles could be obtained without foaming.

By spinning these pellets using a conventional melt I7j method and then drawing them, a drawn yarn of 75 denier and 24 filaments could be obtained without yarn breakage.

This drawn yarn is cylindrically knitted and refined.
Antibacterial properties were evaluated for items that had been washed 0 times.

The bacterial count reduction rate was 97.7% for Escherichia coli in the sample after refinement II.
9% against Staphylococcus aureus, 945% against Staphylococcus aureus, 94.5% against Escherichia coli after washing, and 91.2% against Staphylococcus aureus, all samples have excellent antibacterial effects. [Effects of the Invention] The antibacterial resin crude acid of the present invention satisfies antibacterial properties and moldability at the same time, so its industrial value is extremely high.

Claims (1)

[Claims] At least one selected from silver, copper, zinc, gold and platinum
Hydrous metal oxide particles supporting 0.1 to 20% by weight of seed metal ions and having an average particle size of 10 μm or less,
A resin composition having antibacterial properties, which is contained in a resin in an amount of 0.01 to 20% by weight.