JPS63260810A - Bactericidal zeolite composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled composition capable of keeping excellent bactericidal action over a long period and miscible in a polymer, etc., without lowering the physical properties of the polymer, by impregnating an aqueous solution of a bactericidal metal salt in a solid zeolite particle under specific condition. CONSTITUTION:(A) A solid zeolite particle selected from A-, X- or Y-type zeolite or mordenite having a specific surface area of >=150m<2>/g and an SiO2/Al2O3 molar ratio of <=14 is added to (B) an aqueous solution of a salt of a bactericidal metal such as Ag, Cu and Zn (e.g. AgNO3) and maintained for a prescribed period e.g. at room temperature to support the metal ion on the component A by ion exchange. The amount of the supported metal ion is about <=90% of the ion exchange capacity of the component A. The supported product is filtered, washed with water, dried at 100-500 deg.C under atmospheric or reduced pressure and pulverized.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to metal ions, especially silver, which have a bactericidal effect.

The present invention relates to a bactericidal zeolite composition comprising solid zeolite particles supporting copper or zinc ions, and a method for producing the same.

[Conventional technology]

It has been known for a long time that silver ions, copper ions, zinc ions, and the like have antibacterial properties. For example, silver ions have been widely used as disinfectants and disinfectants in the form of silver nitrate solutions. However, the solution form is inconvenient in handling and 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 for holding metal ions in polymers, such as methods of adhering or adding thin metal wires or powder to polymers, and methods of incorporating metal compounds into polymers. There is. However, the method of using the metal itself has the disadvantage that the specific gravity and Young's modulus of the metal are significantly higher than those of ordinary polymers, so it is poorly compatible with the polymer, and it also requires a relatively large amount, which increases the weight and The cost will be high. On the other hand, methods that use metal compounds either have a large effect on the polymer and severely limit the scope of their use, or even if this is not the case, the metal ions are simply contained in the polymer or are simply added to the polymer. Because it is not too thick, it often falls off during use, causing problems with the sustainability of its sterilizing effect. As a method with fewer such drawbacks, a method has been proposed in which a polymer contains an organic functional group having ion exchange ability or a complex forming ability, and a metal ion is bonded to the organic functional group. However, even in this method, 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 an organic functional group-containing compound is added to the polymer, the interaction between the organic functional group and the polymer cannot be ignored. In order to avoid drastic changes in physical properties, the type of polymer and the type of organic functional group must be selected within a very narrow range.

20 to 30 zeolites saturated with copper, zinc, silver, etc.
There is a known marine paint containing 1% (French Patent No. 1061158). However, although this paint is suitable for exterminating shellfish and algae, it was found that its bactericidal properties were not satisfactory.

This will be explained in detail in Example 4 later.

[Problem to be solved by the invention]

An object of the present invention is to provide a means for maximizing the bactericidal properties of bactericidal metal ions and expanding the field of use thereof. In other words, we are developing a method for sterilization that uses a small amount of sterilizing metal ions to stably exhibit excellent sterilizing properties over a long period of time, and that reduces the physical properties of other substances, such as polymers, when mixed with them. The invention provides.

[Means to solve the problem]

The present invention provides zeolite solid particles having a specific surface area of 150 Td/g or more and a Si 02 /A1203 molar ratio of 14 or less, and zeolite solid particles having a concavity of about 90% or less of the ion exchange capacity of the zeolite solid particles. A germicidal zeolite composition consisting primarily of germicidal metal ions supported by exchange.

The present invention also provides a method for producing the above-mentioned bactericidal zeolite composition, which comprises impregnating zeolite solid particles with an aqueous solution of a bactericidal metal salt under conditions that do not precipitate metal compounds. Provided is a method characterized in that zeolite is made to support sterilizing metal ions in an amount of about 90% or less of the ion exchange capacity on zeolite by ion exchange.

In the present invention, biolite solid particles carrying germicidal metal ions (hereinafter sometimes referred to as germicidal zeolite solid particles for simplicity) mean that natural or synthetic zeolite made of aluminosilicate supports germicidal metal ions.
It supports one species or two or more species through ion exchange.

Suitable examples of germicidal metal ions include silver, copper and zinc ions.

Zeolite is generally an aluminosilicate with a three-dimensionally developed skeleton structure, and is generally based on 81203. 203”ys
It is expressed as f 02 ·Z H20.

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 coefficients of metal oxide and silica, respectively, and 2 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 present invention must be 150 TIi/g (based on anhydrous zeolite).

A solution of water-soluble salts of silver, copper, and zinc 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 combination. Zeolite particles carrying metal ions can be supported on a stationary phase, but
Specific surface area is 150Trt/g or more, and S i 02
/ A, ll 203 Two conditions must be met: the 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 immobilized on the zeolite is insufficient to produce the desired effect. In other words, this is considered to be attributable to the physicochemical properties such as the amount of exchange groups, exchange rate, and accessibility of Biolye 1 to 1.

Therefore, S! is known as molecular sieve.
Zeolites with a high molar ratio of 02/A j 203 are completely unsuitable for the present invention.

S again! 02 / Afl 203 In zeolite with a molar ratio of 14 or less, it is possible to uniformly support metal ions that have a bactericidal effect, and a sufficient bactericidal effect can only be obtained by using such a zeolite. It turned out that. In addition, zeolite S i O2/Afl. The acid resistance and alkali resistance of zeolite with a high silica ratio exceeding 14 is Sio
2 increases, but on the other hand, it also takes a long time to synthesize, and it is not economically advisable to use zeolite with such a high silica ratio. The aforementioned S t 02 /
A, I! Natural or synthetic zeolites with a ratio of 203≦14 can be used satisfactorily from the viewpoint of acid resistance and alkali resistance in the fields in which the present composition is normally used, and are economically advantageous as they are inexpensive. From this meaning, S!
02/Afl203 molar ratio must be 14 or less.

As the zeolite material having a S f 02 /AI 203 molar ratio of 14 or less used in the present invention, any natural or synthetic olide can be used. For example, natural zeolite is analcime (Analcime).
S i 02 /AJ2203 = 3.6 to 5.6
), Chabazite (S t
02/A, ll2o3=3.2-6.0 and 6.
4-7.6), clinoptilolite (C1inopti
lolite: S i O2/A, ll203=8
．． 5-10.5), Erionite
:S! 02/Afl 203 = 5.8
~7.4), aujasite:
S i 02 /AfI203 = 4.2 to 4.6), mordenite (lIlordenite: S ! O /
A, I2203 =8.34~10.0>, Hui! J
”/Phillipsite:S i 0
2 /AN 203 =2.6 to 4.4). These typical natural zeolites are suitable for the present invention. On the other hand, typical synthetic zeolites include 8-
type zeolite (S i 02 /A, Q 203-1.
4-2.4), X-type zeolite (S f 02 /
AN 203 = 2-3), Y-type zeolite (S
t 02 / AM 203 = 3-6), mordenite (S i 02 /AI! 203 = 9-10)
These synthetic zeolites are suitable as the zeolite material of the present invention.

Particularly preferred are synthetic octa-zeolites, X-zeolites, Y-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. When the sterilizing zeolite of the present invention is mixed into a thick molded body, such as various containers, pipes, granules, or thick denier fibers, the particle size is from several microns to several tens of microns or several tens of microns.
The particle size may be 0 micron or more, but when forming into -5 fine denier fibers or films, the smaller the particle size, the better; for example, in the case of clothing fibers, the particle size is preferably 5 microns or less, particularly 2 microns or less.

Metal ions must be supported on zeolite solid particles by an ion exchange reaction. The metal ions should be ion-exchanged in an amount less than, especially about 90% of, the ion-exchange capacity of the zeolite solid particles. If metal compounds are simply adsorbed or adhered without ion exchange, or if ions are exchanged beyond saturation, the bactericidal effect and its sustainability will be insufficient. As a method for retaining metal ions, various zeolites defined in the present invention are used as A(]-
An example of conversion to zeolite will be explained.

Usually, a solution of a water-soluble silver salt such as silver nitrate is used in Ag-zeolite conversion, but care must be taken not to increase the concentration thereof. For example, 8-type or
When converting type zeolite (sodium type) to Ac1-zeolite using an ion exchange reaction, when the silver ion concentration is high (for example, when using 1 to 2M AqNO3), the silver ions are converted to sodium in the same phase by ion exchange. At the same time as it replaces ions, it precipitates as silver oxide in the same phase of zeolite. 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, the bactericidal power decreases due to the presence of silver oxide itself.

In order to prevent such excessive silver from being deposited on the biolite phase, the concentration of the silver solution must be diluted, for example 0.3M.
It is necessary to maintain AgNO3 or less.

In this case, the specific surface area of the A(]-zeolite obtained was almost the same as that of the original seolide, and it was found that the bactericidal effect could be exhibited under optimal conditions.

Next, when the zeolite defined in the present invention is converted to Cu-zeolite, the same phenomenon as that of AQ-zeolite described above occurs depending on the concentration of the copper salt used for ion exchange. For example, 8- or X-type zeolites (sodium-
type) to Cu-biolite by ion-exchange reaction, when using 1MCu S04, cu''+ replaces Na+ in the solid phase, but at the same time, Cu3 (304) (OH4 ) The porosity of the zeolite decreases due to the precipitation of basic precipitates such as It is preferable to maintain the concentration of the prepared solution in a more dilute state, for example, 0.05 M or less.When using a CuSO4 solution with such a concentration, the specific surface area of the Cu-zeolite obtained is almost the same as that of the original biolite, and the bactericidal effect is optimal. It was found that there are advantages that can be demonstrated under certain conditions.

It has been mentioned that during conversion to Ag-zeolite and Cu-zeolite, solid matter may precipitate on the zeolite solid phase depending on the concentration of salts used for ion exchange.
When converting to n-zeolite, the salts used are 2
This phenomenon is not observed in the vicinity of ~3M. Generally, the 7-n-zeolite used in the present invention can be easily obtained by using salts having concentrations around the above range.

The above-mentioned Ag-zeolite, Cu-zeolite and Zn-
When carrying out the ion exchange reaction for conversion to zeolite in a batch method, 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 batch treatments can 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 desired metal-zeolite material can be easily obtained by filling an adsorption tower with the zeolite material and passing the salt solution through it. is obtained.

The amount of metal in the above metal-zeolite (based on anhydrous zeolite) is 30% by weight or less for silver,
The preferred range is from 0.00% to 5% by weight. on the other hand,
Regarding copper and zinc, the amount of copper or zinc in the metal-zeolite (based on anhydrous zeolite) is up to 35% by weight, with a preferred range of 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% or less based on metal-zeolite (based on anhydrous zeolite);
The preferred range depends on the composition ratio of metal ions, but is approximately o, ooi to 15% by weight.

Further, 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.

The bactericidal zeolite composition of the present invention is subjected to a drying treatment, if necessary, before use. Drying conditions are normal pressure or reduced pressure 100~
It may be selected appropriately within the range of 500°C. Preferred drying conditions are 100 to 350°C under reduced pressure.

The bonding force between the zeolite defined in the present invention and silver, copper, and zinc ions is extremely large, unlike a method in which the zeolite is held by an adsorbent such as activated carbon or alumina simply by physical adsorption. The strong germicidal ability of articles containing such metal-zeolites, such as polymer moldings, and their long-term persistence are therefore to be noted as characteristic advantages of the present invention. The biolite limited as in the present invention has a bactericidal effect.
.

It has the advantage of high reactivity with Cu and 7-units. For example, A
-type zeolite, X-type zeolite, Y-type zeolite, ion exchangeable metal ions (Na
> easily undergoes ion exchange with Aq, Cu, "" or Zn, and the metal ions are supported in the zeolite matrix. In addition, the zeolite limited as in the present invention is
It has the advantage of high selective adsorption for Ag, Cu2+ and Zn2+. This fact indicates that even when the polymer composition containing sterilizing zeolite particles of the present invention is used in liquids or water containing various other metal ions for the purpose of sterilization, ACJ
, Cu2+/Zn2+ is stably supported in the zeolite matrix for a long period of time and does not elute, meaning that the bactericidal activity is maintained for a long period of time.

In addition, the zeolite defined as in the present invention has a large exchange capacity and has bactericidal activity.

There is an advantage that the amount of supported Cu and zn ions can be increased. In addition, depending on the purpose of use of the bactericidal zeolite composition of the present invention, Ai7, C supported on zeolite solid particles may be used.
There is an advantage that the amount of tl and ln ions can be easily adjusted by ion exchange.

Furthermore, when the sterilizing zeolite defined in the present invention is mixed into a polymer, it hardly deteriorates the physical properties of the polymer, and can be mixed into various polymers.

Furthermore, the bactericidal zeolite composition of the present invention can be widely applied to antibacterial paints, coatings, tile joints, and the like.

Furthermore, since the bactericidal biolite composition of the present invention also has the original functions of zeolite, it is possible to utilize both antibacterial properties and the original functions of zeolite.

For example, the combined effect of zeolite's original functions of moisture absorption and adsorption and antibacterial effects can be utilized.

It is also possible to coexist with other functional substances to exhibit a combined function of the above effects and other functions. Other functional substances include activated carbon and silica gel.

In the case of activated carbon, the deodorizing and adsorption effects are enhanced, and in the case of silica gel, the moisture absorption effect is enhanced.

Next, examples of the present invention will be described, but the present invention is not limited to these examples unless the gist thereof is exceeded. In the Examples, the bactericidal effect was evaluated by the following test method.

(1) Test method for evaluating antibacterial activity An antibacterial activity test was conducted using the disk method. That is, a sterilizing zeolite composition is mixed into a polymer to make a molded body,
It was cut into a disk with a diameter of 20 TrL/R, which was used as a test disk. Among the bacteria tested, ESCheriCh
ia coli, Pseudomonas aeru
ginosa.

Using 5 taphylococcus aureus,
Candida albicans was used as a fungus. The culture medium is Hueller HintO for bacteria.
For fungi, Sabouraud medium was used. The test bacteria were suspended at 10 8 cells/rd in physiological saline and dispersed in the medium using a 0.1 d Conlage stick. Next, the test disk was pasted onto it.

When determining antibacterial activity, in the case of bacteria, the presence or absence of an inhibition zone is observed after culturing at 37°C for 18 hours, and in the case of -5 fungi, the formation of an inhibition zone is observed after culturing at 30°C for 1 week. The presence or absence of was observed.

(2) Method for measuring fungal mortality rate A polymer molded body containing a bactericidal zeolite composition was immersed in a spore suspension of Aspergillus flavus (7) (104 spores/rr11) and allowed to act at 30°C for 24 hours. Next, the samples were sampled, diluted, dispersed on a Sabouraud agar medium, and kept at 30°C for 24 hours.Next, the number of surviving pieces was measured to determine the mortality rate.

Example 1 Table 1 shows the natural and synthetic zeolite particles used in the examples of the present invention. Each zeolite was made by crushing and classifying crude raw materials to obtain the desired particle size.

In Table 1, 8-type zeolite is abbreviated as 71, X-type zeolite as 72, Y-type zeolite as 73, natural mordenite 1 as 74, natural mordenite 2 as 75, and natural chabasite as 76. These zeolite particle sizes, water content,
The specific surface area was as shown in Table 1.

Next, the fine powder dried product names of various zeolites listed in Table 1 250
Collect 500 d of 1/IOM silver nitrate aqueous solution to each
was added and kept under stirring at room temperature for 3 hours to perform ion exchange. After filtering the silver-zeolite obtained by such ion exchange, 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.

Silver content, specific surface area, and ratio of the amount of ion-exchanged silver to the ion-exchange capacity of the zeolite (%) (hereinafter referred to as ion-exchange saturation %) of the obtained dried silver-zeolite product
are shown in Table 2.

Below, the back of the silver-zeolite conversion product, silver-A type zeolite is 77, silver-X type zeolite is 78, silver-Y type zeolite is 79, silver-natural mordenite 1 is Z1o1 silver-
Natural mordenite 2 is abbreviated as 711, and silver-natural tibasite is abbreviated as Z12.

Example 2 250 g of dried fine powder of four types of synthetic or natural zeolites, Zl, Z3゜Z, and Z6, were collected from among the various zeolites shown in Table 1, and 1.5 g of a 1/20M copper sulfate aqueous solution was added to each. l! added. The resulting mixture was stirred at room temperature for 5 minutes.
Holds time. The copper-zeolite obtained by such ion exchange was suction filtered and washed with water until sulfate ions were removed. Next, add water-washed copper-zeolite to 100 to 10
After drying at 5°C, the product was pulverized to obtain a finely powdered copper-zeolite conversion product.

The copper content, specific surface area, and ion exchange saturation % of the copper-zeolite conversion product obtained by the above method are shown in Table 2.

Among copper-zeolite conversion products, copper-A type zeolite is 2
13. Copper-Y type zeolite is abbreviated as 214, copper-natural mordenite 1 as Z15, and copper-natural jabasite as 216.

Example 3 Dry powder of 8-type zeolite (Zl) shown in Table 1 250
g was collected, and 1fI of 2M zinc chloride solution was added thereto, and the resulting mixture was maintained at around 60'C for 3 hours and 20 minutes with stirring. The zinc-zeolite obtained by such ion exchange was separated by centrifugation. Here, the batch process was repeated four times. The finally obtained converted product was washed with water to remove excess zinc ions. .Then 10
After drying at around 0° C., it was pulverized to obtain a fine powder of zinc-claw type zeolite.

In addition, fine powder dried product 2509 of X-type zeolite (Z2) and natural mordenite 2 (Z5) shown in Table 1 was collected,
The mixture obtained by adding 1 g of 1/20M zinc sulfate solution to each was kept under stirring at room temperature for 5 hours to perform ion exchange. The obtained zinc-zeolite was suction filtered and washed with water until sulfate ions disappeared. Next, the water-washed zinc-zeolite was dried at 100 to 105°C and then ground to obtain a fine powder of zinc-zeolite.

Table 2 shows the zinc content, specific surface area, and ion exchange saturation % of the 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 717, zinc-X type biolite as Zl8, and zinc-natural mordenite 2 as 719.

Usage Example 1 Silver-A type zeolite (Z7), silver-X type zeolite (Z8), silver-Y type zeolite (Z9), or silver-natural mordenite 1 (71o) shown in Table 2 was heated for 200 minutes 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 (ηreN) of 2' measured with 95% sulfuric acid so as to give a concentration of 2% by weight, followed by melt spinning and stretching according to a conventional method to obtain a 120 denier/4 Four types of drawn filament yarns were obtained. Next, the drawn yarn was tube-knitted and refined, and then the bactericidal effect of each yarn was evaluated. Furthermore, in order to check the sustainability of the antibacterial activity, the tubular knitted fabric was tested according to JIS L-0217 (
After washing according to Method 105) and repeating this process 50 times, the antibacterial activity was evaluated. However, for this test, can
+tiaalbicans was used as a test bacterium.

Table 3 shows the evaluation results of the antibacterial activity, Table 4 shows the fungal kill rate, and Table 5 shows the evaluation results of the sustainability of the antibacterial activity.

Table 3 (Evaluation of antibacterial activity) Table 4 (Fungal killing rate) Table 5 (Evaluation of sustainability of antibacterial activity) As is clear from Table 3, the bactericidal polymer composition of the present invention has the following characteristics: It has a bactericidal effect on more than one species of bacteria to be tested. Furthermore, as is clear from Table 4, eight supergillus flavu
The bactericidal activity against S is 90% or more. Furthermore, as shown in Table 5, it was confirmed that the antibacterial activity was maintained even after repeated washing 50 times.

Comparative Example 1 Zeolite Z1 shown in Table 1 that does not support silver ions
．． Z2. Dry fine powder of Z3 or Z4 was added to nylon and spun into 120 denier/spun powder in the same manner as in Example 1.
Four types of 4-filament drawn yarns were obtained. Next, the antibacterial activity of the drawn yarn tube knitted fabric was evaluated and the fungal killing rate was tested using the same method and test bacteria as in Use Example 1. In both cases, no inhibition zone was formed, and the killing rate was It was 0% and no effect was observed.

Use example 2 Copper-A type zeolite (Z13) shown in Table 2, copper-Y
type zeolite (Z14) or copper-natural mordenite 1 (
Z15) was dried at 200° C. for 7 hours under reduced pressure. Next, this was added to polyethylene terephthalate dry chips having an intrinsic viscosity [η) of 0.640 measured in a mixed solvent of phenol/tetrachloroethane (6:4) at a concentration of 10% by weight, and melted at 270°C. After mixing, the mixture was extruded into a gut shape, cooled and cut to obtain three types of master chips. Next, the master chip and the polyethylene terephthalate chip to which no zeolite has been added are dried to a moisture content of O and OI%, and then fed at a ratio of 1:2, and composite spun and drawn to form a 50-denier material with a cross-sectional shape as shown in FIG. Three types of composite yarns each having 15 filaments were obtained. In FIG. 1, A is a polyester component to which sterilizing zeolite has been added, and B is a polyester component to which no sterilizing zeolite has been added.

Next, two of the composite yarns and a 50 denier/36 filament drawn yarn of ordinary lenterephthalate containing no bactericidal zeolite were combined, tube-knitted, and refined, and then subjected to an evaluation test for antibacterial activity against Escherichia coli. As a result, an inhibition zone was formed in each case, confirming the bactericidal effect.

Comparative Example 2 Zeolite Z1. shown in Table 1 that does not support copper ions.
Dried fine powders of Z3 and Z4 were added to and mixed with polyethylene terephthalate in the same manner as in Example 2, and then composite spun to obtain a composite yarn of 50 denier and 15 filaments. When the antibacterial activity of the composite yarn tube knitted fabric was evaluated in the same manner as in Use Example 2, no inhibition zone was formed and no effect was observed.

Comparative Example 3 250g of dry fine powder of A-type zeolite (Zl) shown in Table 1
was collected, and 1 g of 1M copper sulfate aqueous solution was added.

This was kept under stirring at room temperature for 5 hours. The copper-A type zeolite thus obtained was filtered under suction, washed with water until sulfate ions disappeared, dried at 100 to 105°C, and ground to obtain a finely powdered steel-A type zeolite. Cu3 (SO4) (OH)4 was precipitated and mixed in the obtained copper-A type biolite conversion product.

This copper-A type zeolite conversion product was added to polyester and mixed and spun into a composite yarn in the same manner as in Example 2 to obtain a composite yarn of 50 denier and 15 filaments.

When the antibacterial activity of the composite yarn was evaluated in the same manner as in Use Example 2, no inhibition zone was formed and no effect was observed.

Use Example 3 Zinc-A type zeolite (Z17) or zinc-X type zeolite (718) shown in Table 2 was dried at 200° C. for 7 hours under reduced pressure. Next, the first component is acrylonitrile and the second component is acrylonitrile.
The bactericidal zeolite was added to a 25% DMF solution of an acrylic polymer consisting of 10% by weight of methyl acrylate and 1% by weight of sodium allylsulfonate as a third component, so that the concentration of each of the bactericidal zeolites was 5% by weight relative to the polymer. The mixture was wet-spun according to a conventional method, stretched, and then cut to obtain two types of 3 denier x 51M acrylic staples. Next, the stable was spun into a No. 30 single yarn using a conventional method, and then each yarn was refined by tube knitting, and the bactericidal effect was evaluated by measuring the fungal killing rate. The results are shown in Table 6.

Table 6 (Fungal killing rate) As is clear from Table 6, the acrylic fiber to which the zinc-zeolite of the present invention was added was found to have a considerable bactericidal effect.

Comparative Example 4 Zeolite Z that does not support zinc ions shown in Table 1
Alternatively, use the fine powder dry product of Z2. Add and mix it to the acrylic polymer in the same manner as in Example 3, and then spin it into 3 denier x 51
A staple of g was obtained and further spun into a No. 30 single yarn. When the antibacterial properties of the spun yarn tube knitted fabrics were evaluated in the same manner as in Use Example 3, the killing rate against fungi was 0% in all cases, and no effect was observed.

Usage Example 4 Silver-A-type biolite (Z7), silver-natural mordenite 2 (Zll), silver-natural chabasite (Z
12) Copper-natural chabasite (716) or zinc-natural mordenite 2 (Z19) was dried at 200° C. for 7 hours under reduced pressure. Then phenol/tetrachloroethane (6:4
) Various concentrations of total zeolite were added and mixed to polybutylene terephthalate (hereinafter abbreviated as PBT) dry powder with an intrinsic viscosity [η) of 1.10 measured in a mixed solvent, and the mixture was melt-injected at 240°C. It was molded into a circular disk with a diameter of 20 m and a thickness of 3 volumes. When the amount added exceeds 50% by weight, the fluidity during melting was poor and the molded product had an uneven appearance. When the amount added is 50% by weight or less, such problems are less likely to occur, and when the amount added is 40% by weight or less, especially 10% by weight or less, stable physical properties with little variation can be obtained. Next, Table 7 shows the results of evaluating the bactericidal effect of the obtained disks based on the fungal killing rate.

Table 7 (Fungal killing rate) *marked indicates no antibacterial activity It can be seen that a metal ion concentration above a certain amount is required depending on both the metal content of the zeolite and the amount of metal seolide added. The germicidal zeolite particle-containing polymer composition of the present invention that satisfies the required amounts described in the text has good antibacterial activity.

Example 4 This example shows that, contrary to the present invention, when a saturated amount of metal is added to the zeolite that reaches the ion exchange capacity of the zeolite, the bactericidal effect is significantly reduced. Comparative Example (3) here was carried out according to Example 1 of French Patent No. 1,061,158.

The zeolite used in the experiment was commercially available fine mordenite powder (
S i 02 /AN 203-E/L, ratio = approximately 10)
There was a time. First, in order to ensure that the type of metal that can be ion-exchanged in this mordenite is sodium, 2M NaCJ! The mordenite was pretreated and regenerated with an aqueous solution and then washed with water to remove excess NaC,Q. .

0.7M Cu(NO3) in 1Kg of mordenite
Approximately 2 liters of the aqueous solution of 2.2 is added under stirring, then dilute nitric acid is added in portions under continuous stirring until the pH of the mixture reaches a final pH of 3.2.
It was set to 1. The mixture was stirred for an additional 5 hours at room temperature to advance the conversion to copper-mordenite. The copper-mordenite was separated, washed with water to remove excess copper ions, and then dried. Approximately 890 g of dry copper-mordenite was obtained, containing 2.6% (on a dry basis) copper. The 2.6% copper corresponds to 41% of the ion exchange capacity of this mordenite.

0.9M Cu(SO4
) Approximately 2 liters of aqueous solution is added under stirring, then dilute sulfuric acid is added in portions under continuous stirring until the pH of the mixture reaches 2.
It was set as 9. The mixture was stirred for an additional 3 hours at room temperature to advance the conversion to copper-mordenite. The copper-mordenite was separated, an additional 1.5 liters of 0.9M CuSO4 aqueous solution was added, and the above procedure was repeated.

The copper-mordenite obtained from this double treatment was separated, washed with water to remove excess copper ions, and then dried. Approximately 930 g of dry copper-mordenite was obtained, which
．． Contains 5% (dry basis) copper. 4.5% copper corresponds to 71% of the ion exchange capacity of this mordenite.

(3) Comparative Example 1009(7)-E Rudenite with 2M OuS
Approximately 250 mL of O4 aqueous solution was added and stirred for 4 hours. Separate mordenite and add 2M cuso4 aqueous solution at about 250r
nl was added and the above procedure was repeated. When the resulting copper-mordenite was washed with water and dried, it contained 6.3% (dry basis) copper. 6.3% copper is approximately equal to the ion exchange capacity of this mordenite.

The three types of copper-mordenite obtained above and the mordenite without copper were tested for antibacterial activity according to the disk method described above. However, here, copper-mordenite particles were sprinkled on the medium instead of disks. The results are shown in Table 8.

From the above, the zeolite composition that supports sterilizing metal ions through ion exchange with a matrix having less than ion exchange capacity has significantly superior bactericidal properties compared to the case of zeolite that supports ion exchange saturated metals. is clear.

[Brief explanation of drawings]

FIG. 1 shows an example of the cross-sectional shape of a spun-drawn polymer composition.

Claims (1)

[Claims] 1. Specific surface area of 150 m^2/g or more and S of 14 or less
A bactericidal zeolite composition consisting primarily of zeolite solid particles having a molar ratio of iO_2/Al_2O_3 and bactericidal metal ions supported by ion exchange on the zeolite solid particles in an amount of about 90% or less of the ion exchange capacity of the zeolite solid particles. thing. 2. The germicidal polymer composition according to claim 1, wherein the zeolite solid particles are composed of A-type zeolite, X-type zeolite, Y-type zeolite, or mordenite. 3. The germicidal zeolite composition according to claim 1, wherein the germicidal metal ion is selected from the group consisting of silver ions, copper ions, and zinc ions. 4. In the method for producing a bactericidal zeolite composition according to claim 1, the zeolite solid particles are impregnated with an aqueous solution of a bactericidal metal salt under conditions that do not precipitate metal compounds. A method characterized by causing zeolite to support bactericidal metal ions in an amount of about 90% or less of the ion exchange capacity of the particles by ion exchange.