JPS61136530A - Treatment of polymer molding containing zeolite particle - Google Patents

Abstract

PURPOSE:To treat an organic polymer molding containing solid zeolite particles carrying metallic ions having a sterilizing action to stabilize that part of the metallic ions which is made vulnerable to deactivation by heat. CONSTITUTION:A molding comprising an organic polymer (a synthetic polymer which undergoes heat hysteresis during molding, e.g., polyethylene) having solid zeolite particles carrying sterilizing metallic ions (e.g., one or more metallic ions selected from the group consisting of silver, copper and zinc) is treated with an aqueous solution of hydrochlorite and/or hydrogen peroxide. As said zeolite particles, those having a specific surface area >=150m<2>/g and a SiO2/Al2 O3 molar ratio <=14 or those composed of zeolite A, zeolite X, zeolite Y or mordenite are desirable.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for treating a molded body made of a tenki polymer containing zeolite solid particles having a bactericidal effect.

More specifically, the present invention relates to a treatment method for stabilizing metal ions that are easily partially deactivated by heat in a th product molecular body molded product containing zeolite solid particles retaining metal ions having a bactericidal effect.

(Prior Art) It has been known for a long time that silver ions, copper ions, zinc ions, etc. have antibacterial properties. For example, silver ions have been widely used as disinfectants and disinfectants in the form of silver nitrate solutions. Ta. However, the solution form is inconvenient to handle;
It also has the disadvantage of being limited in terms of use. Therefore, if metal ions are retained in a polymer, such drawbacks will be minimized, and it can be expected to be used in a wide range of fields.

Hitherto, a method has been proposed as a method for retaining gold ions in molecular bodies. For example, as a method for incorporating a metal compound into a polymer, JP-A-54-1472
No. 20, etc., have been proposed, but these methods either have a large effect on the polymer and the usable range is severely limited, or even if not, the metal ion is simply contained in the polymer. Since the disinfectant is only attached to the disinfectant, it often falls off during use, and there is a problem with the sustainability of the bactericidal effect. As a method with fewer such drawbacks.

Japanese Patent Publication No. 54-8895 discloses a method in which a polymer contains an organic functional group having ion exchange ability or a complex forming ability, and the organic functional group retains a metal ion.

Japanese Patent Publication No. 57-17108, Japanese Patent Publication No. 58-1769
Publication No. 1770, Japanese Unexamined Patent Publication No. 156074,
This method has been proposed in Japanese Patent Application Laid-Open No. 220877, etc.

However, even in these methods, the interaction between the negative functional group and the polymer can be ignored. Regardless of the addition, the type of polymer, the type of organic functional group, and D must be within a narrow range in order to avoid significant changes in the physical properties of the polymer.

(Problems to be Solved by the Invention) The present inventors have improved the above-mentioned drawbacks and
As disclosed in the above publication, a zeolite particle-containing polymer is composed of zeolite solid particles and an organic polymer, and is characterized in that at least a part of the zeolite solid particles retain metal ions having a bactericidal effect. and proposed its manufacturing method.

The zeolite particle-containing polymer has extremely antibacterial properties.
It was confirmed that it is particularly effective against Escherichia coli and Staphylococcus aureus. However, nylon 6, nylon 66
Or, in the case of polymers such as polyethylene terephthalate, which are made into molten layer molded products at high temperatures, the antibacterial properties are extremely good immediately after they are made into molded products, perhaps because they are affected by heat, but if they are left for a long time. However, depending on the environmental conditions, a decrease in antibacterial properties may be observed. It is thought that some of the metal ions in the zeolite particles have changed.

The present invention relates to a treatment method for stabilizing metal ions in solid zeolite particles contained in a polymer molded article.

(Means for Solving the Problems) The method of the present invention involves treating a molded body made of an organic polymer containing zeolite solid particles having a bactericidal effect with an aqueous solution of hypochlorite and/or hydrogen peroxide. It is characterized by

In the method of the present invention, the zeolite-based solid particles having a bactericidal effect are those in which one or more types of metal ions are retained in the ion-exchangeable part of a natural or synthetic zeolite made of aluminosilicate, waiting for a bactericidal effect. be. As a preferable example of a metal ion having a bactericidal effect, 11. C
Examples include u and Zn. Therefore, for the purpose mentioned above, it is possible to use the above-mentioned metals having bactericidal properties alone or in the form of an island.

Zeolite is generally an aluminosilicate with a three-dimensionally developed skeleton structure, and generally has an X M 2/n OaAz, o3"7810 based on A120a.
It is represented by 2'ZH,0. M represents an ion-exchangeable metal ion, and is usually a monovalent to divalent metal.

n corresponds to this valence. On the other hand, X and y represent the coefficients of metal oxide and silica, respectively, and 2 represents the number of crystal water. Many types of zeolites are known, differing in composition ratio, pore size, specific surface area, etc.

However, the specific surface area of the zeolite solid particles used in the method of the present invention is 150f1f/g (based on anhydrous zeolite) or more, and the zeolite constituent components are 5io2/Al2O3.
The molar ratio should be 14 or less, preferably 11 or less.

Metals with bactericidal properties used in the method of the present invention, such as silver,
A solution of water-soluble salts of copper and curved lead easily undergoes ion exchange with the zeolite defined in the present invention, so utilizing this phenomenon, the necessary metal ions can be added to the zeolite either singly or in a mixed form. Zeolite particles holding Kanejima ions have a specific surface area of 150 m'/1/ or more and 5io2/
Two conditions must be met: the A/203 molar ratio is 14 or less. It has been found that if this is not the case, the object of achieving effective bactericidal action cannot be obtained.

This is thought to be due to the fact that the absolute amount of gold-clad ions fixed to zeolite is insufficient in a state where the effect can be exerted.

In other words, this is considered to be due to the physicochemical properties of the zeolite, such as the amount of exchange groups, exchange rate, and accessibility.

Therefore, 5io, known as molecular sieve
2/l? Zeolites with a high 20* molar ratio are completely unsuitable for the process of the present invention.

In addition, in zeolite with a 5io2/Ag2O3 molar ratio of 14 or less, it is possible to uniformly retain metal ions having a bactericidal effect, and therefore, a sufficient bactericidal effect can only be obtained by using such a zeolite. In addition, zeolite 5io2/A/20. The he and alkali resistance of zeolites with a high silica ratio of which the molar ratio exceeds 14 increases as the 5io2 increases, but on the other hand, it takes a long time to synthesize this, and from an economical point of view, the zeolites with such high silica ratios Encroachment is not a good idea.
45io2/Agzoa514 natural or synthetic zeolite can be used satisfactorily in the fields in which the present structure is normally considered in terms of acid resistance and alkali resistance.
Also, from an economic point of view, it is inexpensive and advantageous. In this sense, the molar ratio of 5io2/1tos must be 14 or less.

As the zeolite material having a molar ratio of 5i02/A#zOa of 14 or less to be used in the method of the present invention, either natural or synthetic zeolite can be used. For example, natural zeolite is analcin (Analc-:5io2/
AA203=8. f) ~ 5.6), chabasite (
Chaba-zite: 5io2/A403=8
．． 2-6.0 and 6.4-7.6), Clinoptilolite: 5io2
/A403=8.5~], 0.5), Erionite (Erionite: qio2/An203=5
．． 8-7.4), Fau, jasi
te: 5io2/Ad203 = 4.2~4.6
), mordenite: 3i
o2/AA'203=8.84~10.0), Phillipsite: 5io2
/Ae2o3=2.6~4.4), etc.

These classic natural zeolites are well suited for the inventive method, while synthetic zeolites are typically A.
-type zeolite (sio2/A1203=L, 4-2
．． 4), X-type zeolite (sio2/Ag203=
2-B), Y-type zeolite (sio2/Ae20
: = 3~6), mordenite (5io2/A1
203=9-10), but these synthetic zeolites are preferred as zeolite materials for the method of the present invention.
It is. Particularly preferred are synthetic A-type zeolites, X-W zeolites, Y-type zeolites and synthetic or natural mordenites.

The shape of the zeolite is preferably in the form of powder particles, and the particle size may be appropriately selected depending on the application. Thick bodies are, for example, containers, pipes, granules, or thick denier keys.
If the particle size is to be used in other products, the particle size may be from several microns to 100 microns or more.On the other hand, if the particle size is to be formed into fine denier fibers or films, the smaller the particle size is, for example, in the case of wR fibers for clothing. is preferably 5 microns or less, particularly 2 microns or less.

The ahecrystalline molecules used in the method of the present invention are synthetic halide molecules that undergo thermal hysteresis during molding, and are not particularly limited. Q: Eha polyethylene, polypropylene,
polystyrene, polyvinyl chloride, polyvinylidene chloride,
Polyamide, polyester, polyvinyl alcohol, polycarbonate, polyacetal, AB S m resin,
Heat, plastic synthetic single molecules such as acrylic resin, fluororesin, polyurethane elastomer, polyester elastomer, thermosetting synthetic polymers such as phenol tree manure, urea tree manure, melamine resin, unsaturated polyester resin, epoxy resin, urethane resin, etc. can be mentioned. When a sterilizing effect of ~1 is required, it is preferable that the surface area of the molded product is large, and one possible method is to mold it into a fiber shape. From this point of view, preferred organic polymers are fiber-forming polymers, such as nylon 6 and nylon 6.
6. Synthetic polymers include polyvinylalcoat, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polybutylene terephthalate, polyacrylonitrile, polyethylene, polypropylene, and copolymers thereof.

The zeolite particle-containing polymer of the method of the present invention is composed of such zeolite solid particles and an organic polymer, and at least a portion of the zeolite solid particles retain metal ions having a bactericidal effect. ing. The proportion of zeolite solid particles in the whole is 0.01 to 50% by weight (
Anhydrous zeolite standard). If it is below the above lower limit, the bactericidal effect is unsatisfactory. On the other hand, even if the above-mentioned upper limit is exceeded, the bactericidal effect remains almost unchanged, and the physical properties of the polymer material change significantly, limiting its use as a polymer molded product. From this point of view, a more preferable content range is 0.
The amount is preferably from 0.05 to 40% by weight, and when the particle-containing polymer of the present invention is used in the form of fibers, it is preferably from 0.05 to 10% by weight.

Metal ions must be retained in the zeolite solid particles through an ion exchange reaction. If the metal ions are simply adsorbed or attached without ion exchange, the bactericidal effect and sustainability will be insufficient.An example of a method for retaining metal ions is to convert each yuzu zeolite to 9-zeolite. In terms of m'MAM-zeolite conversion, water-soluble silver salt BA such as silver nitrate is used, but care must be taken not to increase the concentration of BA.

For example, when converting A-type or
When using Ml'HO1) silver ions replace sodium ions in the solid phase by ion exchange, and at the same time, silver oxides etc. are precipitated in the zeolite solid phase. This has the disadvantage that the porosity of the zeolite is reduced and the specific surface area is significantly reduced.

Furthermore, even if the specific surface area does not decrease significantly, silver oxidation
The bactericidal power decreases due to the presence of the substance itself. In order to prevent such excess silver from being deposited on the zeolite phase, the concentration of the silver solution should be diluted, for example, 0.8 MAf/NO.

It is necessary to maintain the following. The safest AfNO
The concentration of s is Q, 1M or less. Ayyo at such a concentration
3f! When BfPt is used, the specific surface area of the Ag-zeolite obtained is almost the same as that of the zeolite used as the conversion material, and the killing effect can be exhibited under optimal conditions.

Next, when zeolites are converted to Cu-zeolite, the same phenomenon as in the case of AI-zeolite described above occurs depending on the concentration of the copper salt used for ion exchange. For example, eight
When converting type or X-type zeolite (sodium-type) to Cu-zeolite by ion exchange reaction, I
When using M(!usO4, Cu”+ is replaced with Ma+ in the solid phase, but at the same time Cu3(S
Due to the precipitation of basic precipitates such as O2)(OH)4, the porosity of the zeolite is reduced and the specific surface area is significantly reduced. In order to prevent such excessive precipitation of buttons on the zeolite phase, it is preferable to keep the concentration of the aqueous preparation used in a more dilute state, for example, 0.05M or less.

When using a Cu804 solution with such a concentration, the Cu obtained
-The specific surface area of zeolite is almost the same as that of zeolite, which is the conversion material, and has the advantage of being able to exhibit its bactericidal effect in an optimal state.

When converting to Zn-zeolite, no precipitation of solids into the zeolite surface phase is observed when the salt used is around 2 to 8M. Zn-zeolite can be easily obtained by using salts having concentrations around the above range.

Af-zeolite, Ou-zeolite and Z as mentioned above
When carrying out the ion exchange reaction by the patch method during conversion to n-zeolite, the zeolite material may be immersed in a salt solution having the above-mentioned concentration. In order to increase the gold content in the zeolite material, the number of patch treatments may be increased. On the other hand, when treating a zeolite material by a column method using a salt solution having the above-mentioned degree of separation, it is possible to easily collect the desired metal-zeolite by filling an adsorption tower with the zeolite material and passing the salt solution through it. is obtained.

The metal spear in the above metal-zeolite (based on anhydrous zeolite) has a temperature of less than aoht% with respect to silver, and the preferred range is from o,oot to 5 aoht%. on the other hand,
For copper and zinc, the amount of copper or other metals in zeolite (based on anhydrous zeolite): 95 mt%
The preferred range is from 0.01% to 15%. It is also possible to use silver, copper and other metal ions in combination; in this case, the total amount of metal ions may be 35% or less based on metal-zeolite (based on anhydrous zeolite), and the preferred range is metal ions. Although it depends on the composition ratio of ions, it is approximately 0.001 to 15% by weight.

Furthermore, even if metal ions other than silver, silver, and other metal ions coexist, such as sodium, potassium, calcium, or other metal ions, the sterilization effect will not be hindered, so the residual or coexistence of these ions is not a problem. .

Next, the metal zeolite is added and mixed to the organic polymer so as to achieve the above-mentioned content, and then a molded body is formed. Amount of metal with bactericidal effect on metallic zeolite rAw
t%) and the amount of metallic zeolite relative to the molded body (
, 8wt%) are all related to the bactericidal effect.
If there is a large amount, B needs to be small, and conversely, if there is a small amount, B needs to be increased.

In order to effectively exhibit the bactericidal effect, the value of A'X'B should be adjusted to be 0.01 or more for Gi-9 zeolite and 0.1 or more for Tsugu or Zinc-zeolite. It is desirable.The timing and method of addition and mixing are not particularly limited.For example, 1 method is to add to the raw material monomer and mix it after mixing 1 method is to add and mix it to the reaction intermediate 1 is a method to add and mix it to the polymer at the end of polymerization There are methods such as adding and mixing to a primer pellet and molding, and adding and mixing to a molding dope, such as a spinning dope.Also, after mixing zeolite solid particles in a vehicle to form a slurry.

It may also be mixed into the molten polymer. In short, the most suitable method may be adopted depending on the properties of the polymer used, characteristics of the process, etc. Generally, it is preferable to add and mix the monomer immediately before molding.2 However, in some cases, it is preferable to add and mix the monomer to achieve good particle dispersion. The metal-zeolite may be dried if necessary before being added to the polymer. The drying conditions may be selected as appropriate in the range of 100 to 500"C under normal pressure or reduced pressure. Preferred drying conditions are 100 to 500"C under reduced pressure.
It is 350'C.

As shown in the above, zeolite solid particles holding sterilizing metal ions are mixed with organic molecules, and the resulting mixture is spun into a molded body. Immediately after molding, the molded product is
For 0 days, its antibacterial performance is extremely good. However,
Depending on the environmental conditions, a decline in antibacterial performance may be observed over several months. The cause is unknown, but
It is thought that some of the metal ions in zeolite are destabilized by heat and are therefore more susceptible to the effects of various gases in the atmosphere, ultraviolet rays, etc. In the method of the present invention, In this method, the molded body is immersed in a water gauze containing chlorate and/or hydrogen peroxide at an early stage after molding.

Examples of the curved chlorate used in the method of the present invention include sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and the like. These are usually 0.05% to 1% by weight
immerse the molded body in an aqueous solution of at room temperature to 70"C,
Process for 10-30 minutes.

In addition, in the case of hydrogen peroxide, a 30% aqueous solution is usually added for 5 to 50 m
Use as e/l. However, conditions such as concentration and temperature are not particularly limited, and low concentration and low temperature are sufficient for those with large fibrous surface species.

Further, a mixture of hypochlorite and hydrogen peroxide may be used.

(Effects of the Invention) The antibacterial performance of the molded article treated by the method of the present invention hardly deteriorates even after several months, and it has excellent long-term durability. Metal ions with bactericidal power are dispersed and held within the polymer body using zeolite as a carrier, so compared to methods that use gold 8 itself, the metal ions are widely distributed and the bactericidal effect is inherently greater. Since the metal ions are stabilized, the bactericidal properties can be maintained for a long time with a small amount of gold ions. Moreover, the processing power of μ can be said to be extremely simple and inexpensive.

(Example of actual work) Next, one practical example of the present invention will be described.
Evaluation of the potency effect was carried out by the following test method.

(Measurement of mortality rate of bacteria) Escherichia coli or 5taph
Of ylococcus au-reus! The test bacterial solution was diluted to a concentration of 2 to 4'X'lO'/1 t using a liquid filter. A portion of 0.2 m of this test area was dropped onto the molded body and left to act at 37° C. for 18 hours. 18
After an hour, the molded body was washed with physiological saline to make the entire body 100 m long, and one part of it was dispersed on an agar medium, and the molded body was heated at 37°C for 2 hours.
After holding for 4 hours, the survival rate was calculated by measuring the number of surviving individuals.

Reference Example 1 Unconverted natural and synthetic zeolite particles used in the examples of the present invention are shown in Table 1. Each zeolite was obtained by crushing and classifying birch material to obtain a desired particle size.

The 8-type zeolite in Table 1 is zl, the X-type zeolite is z2, the Y-type zeolite is z3. natural mordenite 1 z4. Natural mordenite 2 is abbreviated as 25, and natural chabasite is abbreviated as z6. These zeolite particle sizes, water content,
The specific surface area was found in Table 1 of the collection.

Next, each of the fine powder dried products of each sand zeolite shown in Table 1 "25"
0& was collected, and 1/1 g M bA acid silver channel solution 500-1 was added to each sample, and the resulting mixture was kept under stirring in M& for 8 hours to perform ion exchange. The edge-zeolite obtained by this ion exchange method was allowed to pass and then washed with water to remove hyperactive silver ions.

Next, heat the zeolite to 100-105°C in the water arf.
After drying, the powder was crushed to obtain a fine powder of silver-zeolite. Among the obtained silver-containing silver-zeolite conversion products of dry sheet-zeolite, silver-A type zeolite was z7, silver-X type zeolite was 28, and m-Y type zeolite was 2. , silver-natural mordenite 1 to 2. . , silver-natural mordenite 2
ll, silver-natural chabasite is abbreviated as z12.

Reference Example 2 2501 pieces of dried fine powder of 4 types of synthetic or natural zeolite were collected from each of the yuzu zeolites listed in Table 1, and 11 pieces of a 1/20 M copper sulfate water bath solution were added to each of them. The resulting mixture was kept under stirring at room temperature for 5 hours. The copper-zeolite obtained by this ion exchange method was filtered with suction and then washed with water until no sulfate ions were present.
The zeolite was dried at 100 to 105°C and then ground to obtain a finely powdered copper-zeolite conversion product.

The copper content and specific surface area of the copper-zeolite converted products obtained by the above method are shown in Table 2. Among the copper-zeolite converted products, copper-A type zeolite is Zls, copper-Y type zeolite is zl. Copper-natural mordenite 1 is abbreviated as zl5, and button-natural chabasite is abbreviated as z and 6.

Reference practical example 3 250f dry powder of 8-type zeolite (2,) shown in Table 1
was collected, 1 all of 2M zinc chloride was added thereto, and the resulting mixture was kept at around 60°C for 3 hours and 20 minutes with stirring. The zinc-zeolite obtained by such ion exchange was separated by centrifugation.

Next, I repeated the process for Mr. Kekikiko. In this preparation method, the batch process was carried out four times. The finally obtained converted product was washed with water to remove excess zinc ions.

Next, the converted product was dried at around 100°C and crushed to obtain a fine powder of zinc-humanoid zeolite.
Collect 250 dried fine powders of Z,) and 1/2 of each
The mixture obtained by adding 0 M zinc sulfate solution Ig was kept under stirring at room temperature for 5 hours to perform ion exchange. The obtained zinc-zeolite was filtered with suction and then washed with water until sulfate ions were removed. Next, the washed zeolite was dried at 100 to 105°C and then ground to obtain a fine powder of zinc-zeolite.

The content and specific surface area of the three types of zinc-zeolite conversion products obtained by the above method are shown in Table 2.

Among the zinc-zeolite conversion products, sacrificial lead-A type zeolite is z, 7. Zinc-X type zeolite (z7), silver-X type zeolite (z8), silver-Y type zeolite (z9) shown in Table 2
), silver-natural mordenite l, 2 (Z,, Zu)
Or silver-natural chabasite (2 pieces) at 200°C under reduced pressure.
It was dried for 7 hours. Next, this was added to and mixed with 6 nylon dry chips having a relative viscosity (ηrel) of 2.8 measured with 95% sulfuric acid at a temperature of 2%, and melt-spun and drawn according to the method to form a 120d/4 filament. A drawn yarn of six types was obtained. Next, the drawn yarn was tube-knitted and refined, and then the bactericidal effect of each yarn was evaluated. In addition, the tube-cloth was soaked in a 0.3 wt% sodium hypochlorite water bath solution at 40'C for 30 minutes.
After being immersed for 0 minutes, it was thoroughly washed with water and its bactericidal effect was evaluated. Furthermore, the fabrics treated with the sodium hypochlorite aqueous solution and the rice-treated fabrics were left in a sunny atmosphere for 3 months continuously, and then the bactericidal effect was tested using Staph as a test bacterium.
ylococcusaureus. Third
The table shows the measurement results of bacterial killing rate.

As is clear from Table 8 and Table 3, those treated with the primary sodium hypochlorite water bath retain their sterilizing performance even after three months of exposure weathering.

Comparative Example 1 Non-silver-converted zeolites z1, z2.2, shown in Table 1
In the same manner as in Example 1, fine powder dried product of Z4 was added to nylon and mixed and spun to obtain four types of drawn yarn of 120 (L/4 filament). After knitting the drawn yarn, Example 1 and Similarly, treatment was carried out with an aqueous solution of sodium hypochlorite, and its sterilizing performance was measured. However, the silver-zeolite described above was melted in the liqueur and fed into the molten 6-nylon polymer that was fed into the spinning head.

The grape-containing slurry was injected using a gear pump. At this time, the slurry was varied in the range of O, Oa to 10 wt% with respect to all the mixed polymer pairs.

After threading it through 20 Shizuko wiring elements in the spinning head, it is extruded from the spinneret, rolled up, and stretched to 50 denier/12. A drawn filament of type 6 was obtained.

Claims (6)

[Claims] (1) A molded body made of an organic polymer containing zeolite solid particles that retain metal ions having a bactericidal effect is treated with an aqueous solution of hypochlorite and/or hydrogen peroxide. A method for processing a polymer molded article containing zeolite solid particles. (2) The method according to claim 1, wherein the zeolite solid particles have a specific surface area of 150 m^2/g or more and a SiO_2/Al_2O_3 molar ratio of 14 or less. (3) The zeolite solid particles are A-type zeolite, X-type zeolite
2. The method of claim 1, wherein the zeolite is comprised of Y-type zeolite, Y-type zeolite, or mordenite. (4) The method according to claim 1, wherein metal ions having a bactericidal effect are retained in the ion-exchangeable portion of the zeolite solid particles. (5) The method according to claim 1, wherein the metal ion having a bactericidal effect is one or more metal ions selected from the group consisting of silver, copper, and zinc. (6) The content of zeolite solid particles is 0.01 to 50
% by weight (based on anhydrous zeolite).