JPH0339335A - Antimicrobial resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition capable of simultaneously satisfying antimicrobial properties and moldability and useful for industrial material, bedding, etc., by blending specific zeolite particles on which a metal ion such as silver or copper is carried with a resin. CONSTITUTION:The aimed composition obtained by blending a zeolite (preferably synthetic zeolite) particles carrying at least one kind of metal ion of silver, copper, zinc, gold and platinum at a weight ratio of 0.1-20% thereon, preferably by ion exchange method and having 25-100 (preferably 30-80) SiO2/Al2O3 molar ratio, >=200m<2>/g (preferably >=250m<2>/g) specific surface area and <=10mum (preferably <=5mum) average particle size with a hydrophilic resin at an amount of 0.01-20wt.% and as necessary adding deodorizing agent, coloring agent, etc., to the blend.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an antibacterial resin composition, and more particularly to an antibacterial resin composition containing 5iOz/8LzO heli-based zeolite particles having antibacterial activity.

[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, the molar ratio of 5102/Aa203 supporting silver, copper, and zinc base ions as an antibacterial agent is 14 or less, and the specific surface area is 1.
Resin containing zeolite particles with a particle size of 50 TIi or more (
Special Publication No. 63-54013@Publication) has been proposed. This resin has excellent antibacterial properties and durability. However, since these particles tend to absorb moisture, there have been problems such as foaming when the particles are blended into a resin, and even after being blended into a resin, the particles tend to absorb moisture, resulting in a decrease in moldability. Therefore, a method of hydrophobizing zeolite particles, that is, a method of coating zeolite particles with liquid paraffin, a silicone-based coating agent, or a fluorine-based resin (JP-A-62-7746N, JP-A-62
No. 7747, Japanese Unexamined Patent Publication No. 62-7748@Publication) have been proposed. However, resins containing such hydrophobically treated zeolide particles have a drawback in that their antibacterial properties are significantly reduced.

[Problems to be Solved by the Invention] The present inventors conducted studies aimed at providing a resin composition free from the above-mentioned problems of antibacterial properties and moldability, and found that SiO
The present invention was completed based on the discovery that a resin containing zeolite particles having a large 2/AQ203 molar ratio and a large specific surface area and a small average particle size is effective.

[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
0% by weight supported, Si 02 /A0.203
Zeolite particles having a molar ratio of 25 to 100, a specific surface area of 200 sum 2/g or more, and an average particle diameter of 10 μm or less,
This can be achieved by using an antibacterial resin composition containing 0.01 to 20% by weight in the resin.

The characteristics of the present invention are that the molar ratio, specific surface area, and average particle diameter of 3i02/AO, zo3 are within a specific range, and silver,
The method uses zeolite particles on which a specific amount of at least one metal ion of copper, zinc, gold, and platinum is supported.

That is, the first feature of the zeolite particles used in the present invention is that they support 0.1 to 20% by weight of at least one metal ion selected from silver, copper, zinc, gold, and platinum; .3 to 15% by weight is preferable, and 0.5 to 15% by weight.
12% by weight is more preferred. If the supported amount of the above metal ions is less than 0.1% by weight, the antibacterial effect of the resin obtained by blending the metal ions will be insufficient; If j exceeds 1%, the antibacterial effect of the resulting resin will be saturated, resulting in a cost disadvantage. In addition to the metal ions of silver, copper, zinc, gold, and platinum, the zeolite particles may support other ions such as ammonium ions depending on the purpose. Also,
In the resulting resin, two
It may contain more than one type of zeolite particles and/or two or more types of zeolide particles having different ion loadings. The metal ions can be supported on the zeolite particles by a conventionally known method, such as an ion exchange method or a method using a volatile metal carbonyl complex, but this is a simple method. Ion exchange method is preferred.

The second feature of the zeolite particles is that the 3i02/A203 molar ratio of the particles is specified to be 25 to 100;
0-80 is preferable, and 35-70 is more preferable. Si
If the O2/A flood 203 molar ratio is less than 25, the moisture adsorption of the zeolide particles is large, resulting in foaming when the particles are blended into the resin, and the moldability of the resulting resin is reduced.
If it exceeds 100%, the water adsorption of the zeolite particles becomes considerably low, but the amount of metal ions carried decreases, and the antibacterial effect of the resulting resin becomes insufficient.

The third characteristic of the zeolite particles is that the surface area of the particles is 20
0 m2/9 or more, preferably 250 m2/g or more, and more preferably 300 Tr12/lj or more. If the surface area of the particles is less than 127 g of 2001T, the amount of metal ions carried by the zeolite particles decreases, and the antibacterial effect of the obtained resin becomes insufficient.

The fourth characteristic of zeolite particles is that their average particle diameter is 10
5 μm or less, preferably 3 μm or less.
A value below μmaX is more preferable.

If the average particle diameter of the particles exceeds 10 μm, the dispersibility of the zeolite particles in the resin will be insufficient, resulting in a decrease in moldability of the resulting resin.

The zeolite particles used in the present invention are mainly 5
It is a crystalline aluminosilicate with a developed three-dimensional skeleton consisting of iOz and A<LzO3.It may be synthetic zeolite or natural zeolite, but it is easily available and of uniform quality. Therefore, synthetic zeolite is preferable. In addition, the zeolite particles used in the present invention have low hygroscopicity and can be incorporated into resins without reducing antibacterial properties due to hydrophobic treatment.
Moreover, since it is possible to carry a sufficient amount of antibacterial metal ions to make the resin exhibit antibacterial properties when blended with the resin, it is possible to obtain a resin composition that has excellent antibacterial properties and moldability at the same time. can.

The resin composition of the present invention must contain 0.01 to 20% by weight of the zeolite particles described above, and 0.05 to 20% by weight.
15% by weight is preferred, and 0.1 to 10% by weight is more preferred. If the content of zeolite particles is less than 0.01% by weight, the antibacterial effect will not be sufficient, and if it exceeds 20% by weight, the antibacterial effect will be saturated, which will not only make it uneconomical, but also reduce moldability.

The resin for containing the zeolite particles described above is not particularly limited, but specific examples include nylon 6 and nylon 66.
Examples include polyesters such as polyamides such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polyethylene and polypropylene, and synthetic resins such as polyvinyl alcohol, acrylic resins, and urethane resins. The more hydrophilic the resin is, the more
In the case of a hydrophobic resin, it is preferable to copolymerize a copolymer component having a hydrophilic functional group or to blend a hydrophilic resin, since the antibacterial effect of the resulting resin will be enhanced.

In the present invention, zeolite particles can be blended into the resin in any manufacturing process, and the resin composition of the present invention includes a degreaser, a deodorant, a flavoring agent, an ultraviolet absorber, an infrared absorber, etc. Depending on the purpose, additives such as additives, flame retardants, fluorescent brighteners, other ionic adsorbents, and other antibacterial agents may be included.

The resin composition of the present invention has not only antibacterial properties but also deodorizing properties 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 fiber core or sheath, and may be mixed, interwoven, interwoven, or blended.

[Example] The present invention will be explained in detail with reference to Examples below. Each characteristic value in the examples was determined according to the following method.

(A) Specific surface area of particles: Measured by evacuating the particles at 500° C. for 2 hours and then adsorbing nitrogen at liquid nitrogen temperature.

(8) Average particle diameter of particles: It was determined from electron micrographs of particles.

(C) 5iOz/A△203 molar ratio of particles: Set by atomic absorption method.

(D) Amount of metal ions supported on particles: It was established using atomic absorption spectrometry.

(E) Antibacterial evaluation of tubular knitted fabric: Test bacteria (Escherichia coli) were added to the tubular knitted fabric.
oil NIHJ or Staphylococcus aureus 5taph
y1ocococcus aereus IFO12γ
32) Suspension buffer was poured into a closed container 150 times/
After shaking for 1 minute and 1 hour, we measured the number of viable bacteria and it was time to go! l! l!
The reduction rate for the number of bacteria in the suspension was determined (shake flask method).

Example 1 Pentasil type zeolite particles (SiOz/A(1z03
Molar ratio=43>100 parts by weight to 0.05 mol 10. The mixture was added to 1,400 parts by weight of an aqueous solution of silver nitrate, and stirred at room temperature for 2 hours. Particles separated by centrifugation were placed on filter paper for 500 min.
By slowly adding 0 parts by weight of deionized water,
Metal ions physically adsorbed on the particle surface were completely washed away. Zeolite particles carrying 2.0% by weight of silver ions (specific surface area 640 m2/!7, average particle diameter 0.7 μm) were obtained by vacuum drying the obtained particles at 150°C for 15 hours.
I got it. 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% by weight of zeolite particles could be obtained without foaming.

By spinning this pellet using a conventional 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.
%, 97.8% against Staphylococcus aureus, 95.3% against E. coli after washing, and 91.8% against Staphylococcus aureus, showing excellent antibacterial effects for all samples. It was found that it has.

Comparative Example 1 Y-type zeolite particles (S[)z/AC203 molar ratio -4
, 3) Using 100 parts by weight, zeolite particles carrying 2.1% by weight of silver ions (
A specific surface area of 680 m2/g and an average particle diameter of 1.0 μm were obtained. When 30 parts by weight of these particles were mixed with 970 parts by weight of nylon 6 using an extruder, foaming was intense;
The resulting pellet contained considerable air bubbles.

When this pellet was spun and drawn in the same manner as in Example 1, yarn breakage occurred frequently and a drawn yarn could not be obtained.

Comparative Examples 2 to 4 Zeolite particles 30 supporting silver ions obtained in Comparative Example 1
After hydrophobicizing the zeolite particles by a known method using various hydrophobic compounds, the zeolite particles were mixed with 970 parts by weight of nylon 6 using an extruder) without foaming. It was possible to obtain a nylon 6 pellet containing 0% by weight.

By spinning this pellet using a conventional 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 tube-knitted and refined, and further 10
Table 1 shows the results of evaluating antibacterial properties for those washed 0 times.

All samples had low antibacterial properties.

Examples 2 to 6 and Comparative Examples 5 to 7 Various types of silver ions were supported in the same manner as in Example 1 using zeolite particles having different zeolide species, specific surface areas, SiO2//1203 molar ratios, and average particle diameters. Zeolide particles were obtained. A pellet formed by blending 3.0% by weight of these zeolite particles with nylon 6 was spun and drawn in the same manner as in Example 1, and then the drawn yarn was cylindrically knitted and refined. Table 2 shows the antibacterial evaluation effect, zeolite particle characteristics, and resin moldability of the washed products.

Example 7 Zeolite particles 30 supporting silver ions obtained in Example 1
When the heavy d part was mixed with 970 parts by weight of modified polyethylene terephthalate (polyethylene terephthalate with a number average molecular weight of 18,000, which is obtained by copolymerizing 5-sodium sulfoisophthalic component M in an amount of 5 mol % based on the total dicarboxylic acid components) using an extruder, foaming occurred. without causing
Modified polyethylene terephthalate pellets containing 3.0% by weight of zeolite particles could be obtained.

After spinning these pellets using the normal melt rP&I7j method, by stretching the pellets, the yarn can be made into 75% fibers without breaking.
A drawn yarn having a denier of 24 filaments could be obtained.

This drawn yarn is tube-knitted and refined, and further 10
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.
%, 94.8% against Staphylococcus aureus, 97.7% against E. coli after washing, and 92.0% against Staphylococcus aureus, showing excellent antibacterial effects for all samples. It was found that it has.

Example 8 Pentasil type zeolite particles (SiO2/AI-zOs
100 parts by weight of molar ratio = 38) was added to 400 parts by weight of a 0.05 mol/vert zinc chloride aqueous solution, and the mixture was stirred at room temperature for 3 hours. Particles separated by centrifugation were placed on filter paper for 500 min.
By slowly adding 0 parts by weight of deionized water,
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 zeolite particles carrying 1.2% by weight of zinc ions (specific surface area 740g/g, average particle diameter 0.7μm).
) was obtained. 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% by weight of zeolite 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 tube-knitted and refined, and further 10
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.
%, 93.2% against Staphylococcus aureus, 94.2% against E. coli and 91.7% against Staphylococcus aureus in the sample after washing, showing excellent antibacterial effects for all samples. had.

[Effects of the Invention] Since the antibacterial resin composition of the present invention satisfies both antibacterial properties and moldability, its industrial value is extremely high.

Claims (1)

[Claims] At least one selected from silver, copper, zinc, gold and platinum
Supports 0.1 to 20% by weight of metal ions, S
An antibacterial resin composition containing 0.01 to 20% by weight of zeolite particles having an iO_2/Al_2O_3 molar ratio of 25 to 100, a specific surface area of 200 m^2/g or more, and an average particle diameter of 10 μm or less. thing.