JPH0360866B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for treating a molded body made of an organic 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 apt to be partially deactivated by heat in an organic polymer molded body containing zeolite solid particles holding 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. . However, in solution form, it is inconvenient to handle and also has the drawback 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. Conventionally, various methods have been proposed as methods for retaining metal ions in polymers. For example, Japanese Patent Application Laid-Open No. 147220/1984 has proposed a method of incorporating a metal compound into a polymer, but these methods have a large effect on the polymer and are extremely limited in their usable range. Although limited, even in cases where this is not the case, metal ions are simply contained in or attached to the polymer, so they often fall off during use, and there is a problem with the sustainability of the sterilizing effect. As a method with fewer such drawbacks, 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 is disclosed in JP-A No. 54-3895 and JP-B-Sho. 57-17108, JP 58-1769, JP 58-1770, JP 58-156074,
This method has been proposed in Japanese Patent Application Laid-Open No. 58-220877, etc.
However, even in these methods, the interaction between the organic functional group and the polymer cannot be ignored, and whether the organic functional group is introduced into the polymer chain or the organic functional group-containing compound is added to the polymer. In any case, in order to avoid significant changes in the physical properties of the polymer, the type of polymer and the type and amount of organic functional groups must be within an extremely narrow range. (Problems to be solved by the invention) The present inventors have improved the above drawbacks and
As disclosed in Publication No. 7361, a zeolite particle-containing polymer is composed of zeolite solid particles and an organic polymer, and is characterized in that at least a portion of the zeolite solid particles retain metal ions having a bactericidal effect. proposed a body and its manufacturing method. It was confirmed that the zeolite particle-containing polymer has extremely high antibacterial properties, and is particularly effective against Escherichia coli and Staphylococcus aureus. However, in the case of polymers such as nylon 6, nylon 66, or polyethylene terephthalate, which are made into molded products after being melted at high temperatures, their antibacterial properties are very good immediately after they are made into molded products, perhaps because they are affected by heat. However, if left for a long time, 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 solid particles having a bactericidal effect are those in which one or more metal ions having a bactericidal effect are retained in the ion-exchangeable part of natural or synthetic zeolite made of aluminosilicate. be. Preferred examples of metal ions having a bactericidal effect include Ag, Cu, and Zn. It is therefore possible to use the above-mentioned bactericidal metals alone or in combination for the above-mentioned purposes. Zeolite is generally an aluminosilicate with a three-dimensionally developed skeleton structure, and is generally XM2/n O・Al ₂ O ₃・ based on Al ₂ O ₃ .
It is expressed as ysio ₂・ZH ₂ O. M represents an ion-exchangeable metal ion, usually a monovalent to divalent metal, and n corresponds to this valence. On the other hand, X and y represent the coefficients of metal oxide and silica, respectively, and Z represents the number of crystallized water. Many types of zeolites are known, differing in their composition ratio, pore diameter, specific surface area, etc. However, the specific surface area of the zeolite solid particles used in the method of the present invention is 150 m ² /g or more (based on anhydrous zeolite), and the sio ₂ /g of the zeolite constituents is
The Al ₂ O ₃ molar ratio should be 14 or less, preferably 11 or less. The solution of water-soluble salts of metals with bactericidal activity, such as silver, copper, and zinc, used in the method of the present invention easily undergoes ion exchange with the zeolite defined in the present invention, so this phenomenon can be utilized to obtain the necessary It is possible to hold the above metal ions alone or in a mixed form in the solid phase of zeolite, but the zeolite particles holding metal ions must have a specific surface area of 150 m ² /g or more and sio ₂ /g. Two conditions must be met: the Al ₂ O ₃ 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 metal ions fixed on the zeolite is insufficient in a state where the effect can be exerted. In other words, the amount of exchange groups in zeolite, the exchange rate,
This is thought to be due to physicochemical properties such as accessibility. Therefore, zeolites with a high sio ₂ /Al ₂ O ₃ molar ratio, known as molecular sieves, are completely unsuitable for the process of the present invention. Furthermore, in zeolite with a sio ₂ /Al ₂ O ₃ molar ratio of 14 or less, it is possible to uniformly retain metal ions that have a bactericidal effect, and for this reason, it is only by using such zeolite that a sufficient bactericidal effect can be achieved. can get. In addition, zeolite _sio2 /
The acid resistance and alkali resistance of zeolites with a high silica ratio (with an Al ₂ O ₃ molar ratio exceeding 14) increase with increasing sio ₂ , but on the other hand, the synthesis of these zeolites takes a long time, and from an economic point of view, such high silica Using zeolite in proportions is not a good idea. sio ₂ /Al ₂ O ₃ mentioned above
≦14 natural or synthetic zeolites can be used satisfactorily from the viewpoint of acid resistance and alkali resistance in the fields in which the present structure is normally considered, and are economically advantageous as they are inexpensive. From this point of view as well, the sio ₂ /Al ₂ O ₃ molar ratio must be 14 or less. The molar ratio of sio ₂ /Al ₂ O ₃ used in the method of the present invention is
As the zeolite material of 14 or less, either natural or synthetic zeolite can be used. For example, natural zeolites include analcime (sio ₂ /Al ₂ O ₃ = 3.6-5.6), chabazite (sio ₂ /Al ₂ O ₃ = 3.2-6.0 and 6.4-7.6), clinoptilolite ( Clinoptilolite: sio ₂ / Al ₂ O ₃ = 8.5 to 10.5), Erionite (Erionite: sio ₂ / Al ₂ O ₃ = 5.8 to 7.4),
Faujasite: sio ₂ /Al ₂ O ₃ = 4.2~
4.6), mordenite (sio ₂ /Al ₂ O ₃ =
8.34~10.0), Philipsite:
_sio2 / _Al2O3 = _2.6-4.4 ). These typical natural zeolites are suitable for the method of the invention. On the other hand, typical synthetic zeolites include A-type zeolite ( _sio2 / _Al2O3 = _1.4-2.4 );
X-type zeolite (sio ₂ /Al ₂ O ₃ = 2-3), Y-
Examples include type zeolite (sio ₂ /Al ₂ O ₃ = 3-6), mordenite (sio ₂ /Al ₂ O ₃ = 9-10), etc.
These synthetic zeolites are suitable as zeolite materials for the method of the present invention. Particularly preferred are
Synthetic A-type zeolite, X-type zeolite, 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 molded products may be from several microns to several tens of microns or several hundred microns or more when applied to various containers, pipes, granular materials, or thick denier fibers, while on the other hand, when molded into fine denier fibers or films, For example, in the case of textiles for clothing, the particle size is preferably 5 microns or less, particularly 2 microns or less. The organic polymer used in the method of the present invention is a synthetic polymer that is susceptible to thermal history during commercialization, and is not particularly limited. For example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyester, polyvinyl alcohol, polycarbonate, polyacetal, ABS resin, allyl resin,
Thermoplastic constituent polymers such as fluorine resins, polyurethane elastomers, and polyester elastomers,
Examples include thermosetting synthetic polymers such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, and urethane resin.
When a high bactericidal effect 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 fibrous shape. From this viewpoint, preferred organic polymers are fiber-forming polymers, such as nylon 6, nylon 66, polyvinyl alkote, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polybutylene terephthalate, polyacrylonitrile, polyethylene, polypropylene, and Examples include synthetic polymers such as copolymers of these. The zeolite particle-containing polymer of the method of the present invention is
It is composed of such zeolite-based solid particles and an organic polymer, and at least a portion of the zeolite-based solid particles retain metal ions having a bactericidal effect. The proportion of zeolite-based solid particles in the whole is 0.01 to 50% by weight (based on anhydrous zeolite). 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 0.05 to 40% by weight, and when the particle-containing polymer of the present invention is used in the form of fibers, a range of 0.05 to 10% by weight is more suitable. Metal ions must be retained in the zeolite solid particles through an ion exchange reaction. If it is simply adsorbed or attached without ion exchange, the bactericidal effect and its sustainability will be insufficient. For example, when converting various zeolites to Ag-zeolite, a solution of water-soluble silver salt such as silver nitrate is normally used to retain metal ions. Care must be taken not to increase the concentration of For example, using A-type or X-type zeolite (sodium-type) using an ion exchange reaction, Ag-
When converting to zeolite, if the silver ion concentration is high (for example, when using 1 to 2 MAgHO ₃ ), silver ions replace sodium ions in the solid phase due to ion exchange, and at the same time silver oxides etc. are generated in the zeolite solid phase. precipitates out. This has the disadvantage that the porosity of the zeolite is reduced and the specific surface area is significantly reduced. Moreover, even if the specific surface area does not decrease much,
The presence of silver oxide itself reduces the bactericidal power.
In order to prevent such excess silver from being deposited on the zeolite phase, the concentration of the silver solution should be diluted, e.g.
It is necessary to keep it below 0.3 MAgNO ₃ . The safest concentration of AgNO ₃ is 0.1M or less. When an AgNO ₃ solution with such a concentration 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 bactericidal effect can be exhibited under optimal conditions. Next, when zeolites are converted to Cu-zeolite, the same phenomenon as in the case of Ag-zeolite described above occurs depending on the concentration of the copper salt used for ion exchange. For example, A-type or X-type zeolite (sodium-type) is converted into Cu-
When converting to zeolite, when using _1MCuSO4 ,
Cu ²⁺ replaces Ma ⁺ in the solid phase, but at the same time, basic precipitates such as Cu ₃ (SO ₄ ) (OH) ₄ are precipitated in the zeolite solid phase, which reduces the porosity of the zeolite. However, there is a drawback that the specific surface area is significantly reduced.
In order to prevent such excessive copper from being deposited in the zeolite phase, it is preferable to maintain the concentration of the water-soluble copper solution used in a more dilute state, for example, 0.05M or less.
When using a CuSO ₄ solution of such a concentration, it is obtained
The specific surface area of Cu-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 solid phase is observed when the salt used is around 2 to 3M. Zn-zeolite can be easily obtained by using salts at concentrations near the above. When carrying out the ion exchange reaction by the patch method in the conversion to the above-mentioned Ag-zeolite, Cu-zeolite and Zn-zeolite, the zeolite material may be immersed in a salt solution having the above-mentioned concentration. In order to increase the metal 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 concentration, the target metal-
Zeolite is obtained. The amount of metal in the above metal-zeolite (based on anhydrous zeolite) is 30% by weight or less for silver, and the preferred range is 0.001 to 5% by weight.
It is in. On the other hand, regarding copper and zinc, the amount of copper or zinc in the metal-zeolite (based on anhydrous zeolite) is 35% by weight or less, and the preferable range is 0.01 to 15% by weight. It is also possible to use silver copper and zinc ions in combination; in this case, the total amount of metal ions may be 35% by weight or less based on the metal-zeolite (based on anhydrous zeolite);
The preferred range depends on the composition ratio of metal ions, but is approximately 0.001 to 15% by weight. Furthermore, even if metal ions other than silver, copper, and zinc, such as sodium, potassium, calcium, or other metal ions, coexist, the bactericidal effect is not 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 have the above-mentioned content, and then a molded body is formed. The amount of metal with a bactericidal effect on the metal zeolite (denoted as Awt%) and the amount of the metal zeolite in the molded body (denoted as Bwt%) are both related to the bactericidal effect; if A is large, B may be small; Conversely, if A is small, B needs to be large. In order to effectively demonstrate the bactericidal effect, A×B
It is desirable to adjust the value so that it is 0.01 or more in the case of silver-zeolite, and 0.1 or more in the case of copper or zinc-zeolite. The timing and method of addition and mixing are not particularly limited. For example, a method of adding and mixing to raw material monomers and polymerizing them, a method of adding and mixing to reaction intermediates, a method of adding and mixing to the polymer at the end of polymerization, a method of adding and mixing to polymer pellets and molding, a method of adding and mixing to polymer pellets and molding, and adding a molding dope, such as a spinning stock solution. There are methods such as addition and mixing. Alternatively, the zeolite solid particles may be mixed into a vehicle to form a slurry, and then mixed into the molten polymer. In short, the most suitable method may be adopted depending on the properties of the polymer used, the characteristics of the process, etc. Usually, a method of adding and mixing just before molding is suitable. However, in some cases it may be preferable to add it to the monomer for better particle dispersion. The metal-zeolite may be dried if necessary before being added to the polymer. Drying conditions may be appropriately selected from the range of 100 to 500°C under normal pressure or reduced pressure. Preferred drying conditions are 100-350℃ under reduced pressure.
It is. As described above, zeolite solid particles holding metal ions having bactericidal properties are mixed with an organic polymer, and the mixed melt is spun into a molded body. The antibacterial performance of the molded product is extremely good for several tens of days immediately after molding. However, depending on the environmental conditions, a decline in antibacterial performance may be observed over several months. Although the cause is unknown, it is thought that some of the metal ions in the zeolite are destabilized by heat, making it more susceptible to the effects of various gases in the atmosphere, ultraviolet rays, etc. In the method of the present invention, the molded product is immersed in an aqueous solution of subzincate and/or hydrogen peroxide at an early stage after molding. Examples of the hypochlorite used in the method of the present invention include sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and the like. these usually
The molded body is immersed in an aqueous solution of 0.05% to 1% by weight at room temperature to 70°C and treated for 10 to 30 minutes. In the case of hydrogen peroxide, a 30% aqueous solution is usually used in an amount of 5 to 50 ml. However, conditions such as concentration and temperature are not particularly limited, and low concentration and low temperature are sufficient for fibrous materials with a large surface area. 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 sterilizing power are dispersed and held within the polymer body using zeolite as a carrier, so compared to methods that use the metal itself, the metal ions are widely distributed and have a greater sterilizing effect. As the metal ions are stabilized, the bactericidal properties can be maintained for a long period of time with a small amount of metal ions. Moreover, the processing method for this purpose can be said to be extremely simple and inexpensive. (Example) The following example of the present invention will be described. In the example, the bactericidal effect was evaluated by the following test method. (Measurement of bacterial mortality rate) Escherichia coli or Staphylococcus au−
Using a suspension of M. reus, the test bacterial solution was 2 to 4 x 10 ⁵
The dilution was adjusted so that it was 100ml/ml. This test bacterial solution 0.2
ml was dropped onto the molded body and kept at 37℃ for 18 hours.
I let time work. After 18 hours, the molded bodies were washed with physiological saline to make a total volume of 100 ml, and 1 ml of the volume was dispersed in an agar medium, kept at 37°C for 24 hours, and the number of viable specimens was measured to calculate the mortality rate. Reference Example 1 Table 1 shows unconverted natural and synthetic zeolite particles used in the examples of the present invention. Each zeolite was obtained by crushing and classifying crude raw materials to obtain the desired particle size. The A-type zeolite in Table 1 is abbreviated as Z ₁ , the X-type zeolite as Z ₂ , the Y-type zeolite as Z ₃ , natural mordenite 1 as Z ₄ , natural mordenite 2 as Z ₅ , and natural chabasite as Z ₆ . The particle diameter, water content, and specific surface area of these zeolites were as shown in Table 1. Next, 250 g of dried fine powder of each type of zeolite listed in Table 1 was collected, and 500 g of a 1/10M silver nitrate aqueous solution was added to each.
ml was added and the resulting mixture was kept under stirring at room temperature for 3 hours to perform ion exchange. After the silver-zeolite obtained by this ion exchange method was filtered, it was washed with water to remove excess silver ions. Next, the water-washed silver-zeolite was dried at 100 to 105°C and then ground to obtain a fine powder of silver-zeolite.
The silver content and specific surface area of the obtained dried silver-zeolite product were as shown in Table 2.

[Table] Among silver-zeolite conversion products, silver-A type zeolite is _Z7 , silver-X type zeolite is _Z8 , silver-Y type zeolite is _Z9 , silver-natural mordenite 1 is _Z10 , silver-natural Mordenite 2 is abbreviated as Z ₁₁ and silver-natural chabasite is abbreviated as Z ₁₂ . Reference Example 2 250 g of dried fine powder of four types of synthetic or natural zeolites were collected from among the various zeolites listed in Table 1, and one portion of a 1/20M copper sulfate aqueous solution was added to each. The resulting mixture was kept under stirring at room temperature for 5 hours. The copper-zeolite obtained by this ion exchange method was suctioned and washed with water until sulfate ions were removed. Next, add the washed copper-zeolite
After drying at 100-105°C, the product was pulverized to obtain a finely powdered copper-zeolite conversion product. Table 2 shows the copper content and specific surface area of the copper-zeolite conversion product obtained by the above method. Among copper-zeolite conversion products, copper-A type zeolite
_Z13 , copper-Y type zeolite is abbreviated as _Z14 , copper-natural mordenite 1 is abbreviated as _Z15 , and copper-natural chaabasite is abbreviated as _Z16 . Reference Example 3 Dry powder of A-type zeolite (Z ₁ ) shown in Table 1
250 g was collected, and 2M zinc chloride solution 1 was added thereto, and the resulting mixture was kept at around 60° C. for 3 hours and 20 minutes while stirring. The zinc-zeolite obtained by such ion exchange was separated by centrifugation.
Next, the same process as above was repeated. 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 zinc conversion product was dried at around 100°C and then ground to obtain a fine powder of zinc-A type zeolite. In addition, 250 g of dried fine powders of X-type zeolite (Z ₂ ) and natural mordenite 2 (Z ₅ ) shown in Table 1 were collected, and 1/20 M zinc sulfate solution was added to each of them to form a mixture. The mixture was kept under stirring at room temperature for 5 hours to perform ion exchange. The obtained zinc-zeolite was suctioned and washed with water until sulfate ions were removed. Next, add water-washed zinc-zeolite to 100~
It was dried at 105°C and ground to obtain a fine zinc-zeolite powder. Table 2 shows the zinc content and specific surface area of three types of zinc-zeolite conversion products obtained by the above method. Among the zinc-zeolite conversion products, zinc-A type zeolite is abbreviated as _Z17 , zinc-X type zeolite as _Z18 , and zinc-natural mordenite 2 as _Z10 .

[Table] Example 1 Silver-A type zeolite (Z ₇ ), silver-X type zeolite (Z ₈ ), silver-Y type zeolite (Z ₉ ), silver-natural mordenite 1,2 ( _Z10 , _Z11 )
Alternatively, silver-natural chabasite was dried using Z ₁₂ under reduced pressure at 200°C for 7 hours. Next, this was added to and mixed with 6 nylon dry chips with a relative year (ηrel) of 2.3 measured with 95% sulfuric acid to give a concentration of 2 wt% each, and after melt-spinning and stretching according to a conventional method, six types of 120D/4 filaments were obtained. A drawn yarn 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 knitted fabric was treated with 0.3wt% of sodium subzinc chlorate.
After being immersed in an aqueous solution at 40°C for 30 minutes, it was thoroughly washed with water and its bactericidal effect was evaluated. Furthermore, after leaving the treated and untreated fabrics treated with the sodium hypochlorite aqueous solution in a sunny atmosphere for three months, the bactericidal effect was tested using test bacteria.
This was done using Staphylococcus aureus. Table 3 shows the results of measuring the mortality rate of sterilization.

[Table] As is clear from Table 3, those treated with an aqueous solution of sodium hypochlorite retain their sterilizing performance even after three months of exposure weathering. Comparative Example 1 Zeolite converted to silver powder shown in Table 1 Z ₁ , Z ₂ ,
_Z3 and _Z4 were each added to nylon and mixed and spun to obtain four types of drawn yarns of 120d/4 filament in the same manner as in Example 1. After the drawn yarn was knitted into a tube, it was treated with an aqueous solution of sodium hypochlorite in the same manner as in Example 1, and its sterilization performance was measured.
The mortality rate was 0%, indicating that the bactericidal effect was not simply due to sodium hypochlorite alone. Example 2 Copper-A type zeolite (Z ₁₃ ), copper-Y type zeolite (Z ₁₄ ), copper-natural mordenite 1 (Z ₁₅ ), copper-natural chiabasite (Z ₁₆ ), zinc-
A-type zeolite (Z ₁₇ ), zinc-X-type zeolite (Z ₁₈ ), and zinc-natural mordenite 2 (Z ₁₀ ) were dried at 200° C. under reduced pressure for 7 hours. Next, this was added to dry polyethylene terephthalate chips having an intrinsic viscosity [η] of 0.640 measured in a mixed solvent of phenol/tetrachloroethane (6:4) to give a concentration of 0.5 wt%.
Melt-spun and stretched at 290℃ according to a conventional method to obtain 50
Seven types of drawn yarns with denier/6 filaments were obtained.
After knitting these into a tube and performing scouring, they were immersed in a 30% hydrogen peroxide solution containing 6 g/aqueous solution at 70° C. and treated for 30 minutes. Table 4 shows the results of measurement and evaluation of these sterilizing performances and the sterilizing performances after being left in the atmosphere for 5 months in comparison with that of the tubular knitted fabrics that had not been treated with hydrogen sulfur oxide solution.
Escherichia coli was used as a test bacterium.

[Table]
Example 3 The silver-Y type zeolite (Z ₉ ) shown in Table 2 was dried at 200° C. for 7 hours under reduced pressure. Next, 50g of this
The slurry was mixed with 100 g of diethylene glycol adipate having a viscosity of 800 cps at 75°C, and kneaded in an automatic mortar for 24 hours to form a slurry. Using a conventional melt spinning machine, dry 6 nylon chips with a relative viscosity of 2.3 measured with 95% sulfuric acid are melted with a screw, and the molten 6 nylon chips are fed into the spinning head.
The above silver-zeolite-containing slurry was injected into the nylon polymer using a gear pump. At this time, the slurry was varied in a range of 0.03 to 10 wt% based on the total amount of mixed polymers. After passing through 20 Shizuko kneading elements in the spinning head,
It was extruded from the spinneret, wound up, and drawn to obtain six types of drawn yarns of 50 denier/12 filaments. These were knitted into a tube, immersed in a 0.1wt% calcium hypochlorite aqueous solution, and treated at 70°C for 30 minutes. These were left in the air for 3 months. Also, those not treated with calcium hypochlorite were left in the air in the same way. For bactericidal performance evaluation, as a test bacterium
Staphylococcus aureus was used.

【table】

Claims (1)

[Scope of Claims] 1. Treating a molded body made of an organic polymer containing zeolite solid particles that retain metal ions having a bactericidal effect with an aqueous solution of hypochlorite and/or hydrogen peroxide. A method for processing a polymer molded article containing zeolite solid particles, characterized by: 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 ₂ O ₃ molar ratio of 14 or less. 3 Zeolite solid particles are A-type zeolite,
2. The method of claim 1, wherein the zeolite is composed of X-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 method according to claim 1, wherein the content of the zeolite solid particles is 0.01 to 50% by weight (based on anhydrous zeolite).