JPH03205436A - Antibacterial resin composition and synthetic fiber produced therefrom - Google Patents

Abstract

PURPOSE:To obtain an antibacterial resin composition improved in antibacterial properties, a color tone upon coloration and an ability to disperse particles and suited for the production of fibers by mixing a resin with particles of a specified antibacterial zeolite. CONSTITUTION:A zeolite which is an aluminosilicate of a developed three- dimensional skeleton mainly consisting of SiO2 and Al2O3 and has an SiO2 to Al2O3 molar ratio (R) in the range of 14<R<25 is impregnated with 0.1-20wt.% ions of a metal selected from among Ag, Cu and Zn and optionally another antibacterial substance to obtain antibacterial particles of a mean particle diameter of 5mum or less. A synthetic resin such as a polyamide, a polyester, a polyolefin, a polyacrylonitrile or a polyurethane is mixed with 0.01-20wt.% said particles and optionally a matting agent, a deodorizing agent, a colorant, a UV absorber, a flame retardant, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an antibacterial resin composition containing antibacterial zeolite particles and a synthetic fiber comprising the same.

[Conventional technology] Nylon fiber, polyester fiber, polyacrylonyl
Synthetic fibers such as Ril fiber and polio-1-nofin fiber have excellent strength, processability, and easy care properties, so they are used in a wide range of applications such as clothing, bedding, interior decoration, and industrial materials. It is being used.

In recent years, there has been a strong demand for excellent antibacterial properties as one of the comfort functions in these applications.

Various methods are known as means for imparting antibacterial properties to fibers. For example, there is a method in which an antibacterial compound such as an aromatic halogen compound, a quaternary ammonium salt, or an organic nitrogen compound is used as an antibacterial agent, and the antibacterial compound is attached to the fiber through post-processing. However, this method has the problem that the antibacterial agent easily falls off when washed or the like, and is also easily decomposed by heat, resulting in poor durability.

In addition, sio2/AI carries antibacterial metal ions such as silver, copper, and zinc as an antibacterial agent. A method of using zeolite particles having a molar ratio of 0.03 to 14 or less and incorporating them into a resin to form fibers has been proposed in Japanese Patent Publication No. 63-54013, etc., and has demonstrated excellent antibacterial properties.

[Problems to be Solved by the Invention] However, in this method, metal ions carried in the zeolite undergo metallization and oxidation during the process of adding zeolite particles to the resin and the process of spinning yarn, causing the color to change to gray or brown. Since this phenomenon tends to occur, there is a drawback that the color tone of the obtained textile product, for example, the clarity when it is made into a lightly dyed product, is poor. This problem was especially serious when using silver ion-supported zeolite. Also,
The above-mentioned antibacterial zeolite particles have high aggregation properties, so it is difficult to finely disperse them into textile products.Therefore, there are problems in that it is difficult to fully demonstrate the excellent physical properties inherent in the fibers, and troubles occur during melt spinning. There was also the problem that it was easy to occur.

Therefore, the present invention can improve the problems in the conventional technology such as deterioration of color tone due to coloring and poor particle dispersibility, and has excellent antibacterial properties, good color tone and dispersibility, and is suitable for fiber production. The main objective is to provide an antibacterial resin composition.

[Means for Solving the Problem] In order to achieve this object, the present invention provides an antibacterial resin composition containing 0.01 to 20% by weight of antibacterial zeolite particles in the resin, in which the antibacterial zeolite is silver, copper,
O
．． ↓ ~ 20% by weight supported, average particle size is 5 μm or less, and SiO2/A1203 molar ratio (RS/A) is 1
The zeolite is characterized by having a R S/A < 25.

The present invention is characterized by the use of antibacterial zeolite particles having a S+02/AI203 molar ratio and average particle diameter within a specific range, and carrying a specific amount of at least one metal ion of silver, copper, or zinc. It is to use.

That is, in order to exhibit excellent antibacterial properties, the zeolite particles used in the present invention contain ions of specific metals such as silver, copper, and zinc. It is required that the amount supported is 1 to 20% by weight, preferably 0.5 to 18% by weight. If the amount of supported metal ions is too small, the antibacterial effect will not be sufficient, so in order to obtain the desired antibacterial effect, it will be necessary to add an extremely large amount of zeolite particles, which will greatly affect the resin's original properties. This makes it difficult to form into fibers, etc.

On the other hand, if the amount of metal ions supported is too large, the metal ion support approaches saturation, making it difficult to support the specified amount of metal ions on the zeolite, and also causing a large loss of metal ions during metal ion exchange, making it impractical. be.

The antibacterial zeolite particles may support other antibacterial substances in addition to metal ions such as silver, copper, and zinc, depending on the purpose. Further, the antibacterial zeolite contained in the resin may be a combination of two or more types of zeolite particles having different types and amounts of metal ions supported.

Supporting metal ions on zeolite particles is carried out by the usual method,
For example, ion exchange method, volatile 4? This may be carried out by a method using a metal carbonyl complex, among others, a method using ion exchange is preferred.

The zeolite particles used in the present invention are SiO2/81■0
It is important that the 3 molar ratio is greater than 14 and less than 25.

If this SiO2/A1203 molar ratio is less than 1-4, metal ions may be metallized or oxidized and colored when zeolite particles are blended into the resin or when fibers are formed by melt spinning. This phenomenon is likely to occur, so
The resulting textile products tend to have undesirable colors such as gray or brown. Moreover, if it is less than 14, the zeolite particles tend to aggregate, so the number of coarse particles increases in the resin pellets or fiber products, which tends to reduce the spinning properties and the physical properties (strength, etc.) of the resulting fibers.

On the other hand, if it is 25 or higher, the amount of metal ions supported decreases, so in order to obtain a large bactericidal effect, a large amount of antibacterial zeolite particles that support metal ions close to the saturation amount must be blended into the resin. This is necessary, and the excellent physical properties inherent to the base borer are likely to be impaired.

Furthermore, the zeolite particles used in the present invention have an average particle diameter of 5 μm or less, preferably 3 μm or less,
More preferably, it needs to be 1 μm or less. If this particle size is too large, it will be difficult to form it into fibers etc.
This increases the number of troubles such as clogging of the filter in the spinning pack and increase in filtration pressure when the fiber shape is changed, and the physical properties of the obtained fibers also deteriorate significantly.

The zeolite particles used in the present invention are mainly S
It is an aluminosilicate with a developed three-dimensional skeleton consisting of in2 and ^1203, and it may be a synthetic zeolite or a natural zeolite as long as its SiO2/A+203 molar ratio is the above-mentioned specific value. Among these, synthetic zeolite is preferred in terms of ease of availability, uniformity of quality, etc.

Specifically, Chabasite (Ch.abazite)
, Clinopjilolit
Natural zeolite Y type, mordenite type, pentasil type, ferrierite type, beta type, Z SM-5 type, ZSM-11 Examples include synthetic zeolites such as molds, etc., and these S i O 2 / A
If the 1 2 0 3 molar ratio is outside the range of the present invention,
The molar ratio may be adjusted by a method such as dealumination.

The average particle diameter of the zeolite particles was determined by taking electron micrographs and the Si of zeolite 1 particles.
The O 2 /A I 2 O 3 molar ratio may be determined by quantitative determination using atomic absorption spectrometry.

The resin composite according to the present invention contains 0.01 to 20% by weight of the antibacterial zeolite particles, preferably 0.05 to 15% by weight.
It is necessary to contain % by weight. If the zeolite particle content is too low, it is difficult to obtain a sufficient antibacterial effect. On the other hand, if the amount is too large, the fiber performance deteriorates significantly, making it difficult to put it into practical use.

There is no particular restriction on the resin that contains the zeolite particles, and specifically, polyamides such as nylon 6, nylon 66, and nylon 46; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyethylene, polypropylene, etc. Polyolefins include synthetic resins such as polyvinyl alcohol, polyacrylonitrile, and polyurethane. These resins may be a homopolymer or a copolymer, and may also be a monopolymer.

In the present invention, zeolite particles may be blended into the resin in any manufacturing process. The resin also contains matting agents, deodorants, colorants, ultraviolet absorbers, infrared absorbers,
Additives such as flame retardants, fluorescent whitening agents, other ion adsorbents, and other antibacterial agents may be added in combination depending on the purpose.

The antibacterial resin composition of claim 1 is particularly useful in fiber form, and if a fiber form or thermoplastic resin is used as the resin, it can be melt-spun, wet-spun or dry-spun by a conventional method. By doing so, antibacterial fibers can be obtained. This antibacterial resin composition is placed on the fiber surface side and 17
Composite spinning with 8? good.

Further, by coating the fiber surface with the resin composition of claim 1 by a conventional method, an antibacterial fiber having an antibacterial resin layer formed on the fiber surface can be obtained.

The resulting antibacterial fibers can be used in a variety of ways, including clothing and bedding, as well as interior items such as carpets and upholstery, and exhibit deodorizing effects by inhibiting the growth of bacteria. .

[Function] The present invention relates to an antibacterial resin composition, in particular to Hewei fiber, which is formed by containing specific antibacterial particles in which antibacterial metal ions are supported in zeolite. Since the SiO2/Al03 molar ratio of these zeolite particles is higher than 14, the polarity of the surface of the zeolite 1 particles becomes smaller, making it difficult for the zeolite 1 particles to agglomerate. This makes it possible to prevent the generation of coarse particles due to agglomeration of particles during the fiber forming process. Antibacterial fibers with excellent physical properties can be obtained. In addition, by using this zeolite particle,
Discoloration to grayish-black or brownish color caused by metalization or oxidation caused by reduction of metal ions in the addition process to the resin or in the fiber forming process is reduced, making it possible to develop vivid colors in textile products.

However, when the SiO2/Al■03 molar ratio is 25 or more,
Since the antibacterial performance is greatly reduced due to the reduction in the exchange saturation amount of metal ions, it is necessary to set the molar ratio to less than 25 in order to stably support a sufficient amount of metal ions to obtain the desired antibacterial performance. .

The average particle diameter of the antibacterial zeolite particles in the resin composition is 5
If it exceeds 5 μm, the physical properties such as strength and elongation of general synthetic fibers for clothing with a fiber diameter of about 15 to 30 μm will decrease significantly. 1μm in order to fully demonstrate the physical properties inherent in synthetic fibers.
The following is preferable.

[Example] The characteristics in the following examples were measured by the following method.

The amount of metal ions supported on the zeolite particles was determined by quantitative determination using atomic absorption spectroscopy.

In addition, to evaluate the obtained antibacterial performance, test bacteria (
Staphylococcus aureus
The suspension buffer of e+aus [FO12732] was added, and the number of viable bacteria was measured after shaking 150 times/min for ■ hours in a closed container, and the reduction rate relative to the number of bacteria in the added suspension was determined. ●By flask method.

Example 1 Mordenite type synthetic zeolite particles (Sin2/At2
0, molar ratio = 17) was added to 900 parts by weight of a 0.1 mol/l silver nitrate aqueous solution, and the mixture was stirred at room temperature for 2 hours. Particles separated by centrifugation are placed on a 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 antibacterial zeolite particles carrying 8.3% by weight of silver ions.

11 The obtained antibacterial zeolite particles were Pellets containing 5% by weight of ordinary nylon 6 were produced using an extruder and dried by a conventional method. The average particle diameter of the antibacterial zeolite particles in the obtained pellets was 0.5 μm, and almost no coloration was observed.

Next, it is fed to an extruder-type melt spinning machine for 900 m.
The yarn was spun at a speed of /min. At this time, no troubles due to foaming or filter clogging were observed, and the spinning was successful.

The obtained undrawn yarn was stretched 3.35 times by a conventional method, and
A drawn nylon 6 yarn of 0 denier 24 filaments was obtained. This drawing could be carried out well, and the obtained drawn yarn had excellent fiber properties, with a strength of 5.5 g/d and an elongation of 40%.

This drawn yarn was knitted into a tube by a conventional method, refined, and dyed pale blue.

The degree of coloring of the obtained dyed knitted fabric was compared with that of a dyed knitted fabric made from nylon 6 that does not contain antibacterial zeolite.
Coloring caused by antibacterial zeolite 12? It was possible to obtain a dyed knitted fabric with almost no visible color and vivid color development.

In addition, when its antibacterial performance was evaluated before and after washing 10 times, the bacterial reduction rate was 99% before washing and 98% after washing, which was excellent.

Comparative Example I Y-type zeolite particles with a Sin2/At■03 molar ratio of 5 were made to carry 8.4% by weight of silver ions in the same manner as in Example 1 to obtain antibacterial zeolite particles. , added to nylon 6.

The obtained pellets are brownish-gray in color, and the antibacterial zeolite particles contained therein have an average particle size of 3.1 μm, but coarse aggregated particles of several tens of μm are also present.

Using the obtained pellets, melt spinning was carried out in the same manner as in Example 1.
Stretching, knitting, scouring and dyeing were performed.

During this melt spinning, the filter in the spinneret bag and the sand filter layer were significantly clogged, and the filtration pressure inside the pack increased by 2 in a few hours.
The weight exceeded 0.0 kg/car and spinning could not be continued. Also, what is the obtained drawn yarn? The degree is 2.9g
/d, and the elongation was 19%, which was poor in fiber properties. Furthermore, the obtained dyed knitted fabric was discolored to a dull brownish color and lacked sharpness.

Examples 2 to 5 Same as Example 1 except that the Si02/AI■03 molar ratio, zeolite crystal type, silver ion supported amount, volima, and antibacterial zeolite addition amount were changed as shown in Table 1.
It was implemented and evaluated.

The results are shown in Table 1, and it was possible to produce an antibacterial dyed knitted fabric with excellent color tone, antibacterial performance, and fiber properties without any trouble during spinning.

15 [Effects of the Invention] By using the antibacterial composition according to the present invention, antibacterial products having excellent color tone, antibacterial performance, and mechanical properties can be produced without any trouble. Therefore, this antibacterial resin composition is particularly useful for textiles where good color tone is required.

Claims (2)

[Claims] (1) 0.01 to 20 antibacterial zeolite particles in resin
% by weight of the resin composition, the antibacterial zeolite supports 0.1 to 20% by weight of at least one metal ion selected from the group of silver, copper, and zinc, and has an average particle size of 5 μm or less. and SiO_2/Al_2O_3
Molar ratio (R_S_/_A) is 14<R_S_/_A<2
5. An antibacterial resin composition characterized by being a zeolite. (2) A synthetic fiber characterized in that at least a surface portion of the fiber is composed of the antibacterial resin composition according to claim 1.