JPH01257124A - Antibacterial aluminosilicate - Google Patents

Abstract

PURPOSE:To prevent a change in the color of aluminosilicate with the lapse of time while maintaining antibacterial power by substituting antibacterial metal ions, etc., for ions in the aluminosilicate. CONSTITUTION:Ions of one or more kinds of metals selected among alkaline earth metals and Mn and antibacterial metal ions are substd. for part of all of ion exchangeable ions in aluminosilicate to form antibacterial aluminosilicate. The antibacterial metal is selected among Ag, Cu, Zn, Hg, Sn, Pb, Bi, Cd, Cr and Tl. Said aluminosilicate is zeolite or amorphous aluminosilicate.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an antibacterial aluminosilicate and a composition containing the aluminosilicate and a resin, and more particularly to an antibacterial aluminosilicate that does not change color over time. The present invention relates to an acid salt and an antibacterial resin composition.

[Conventional technology]

Conventionally, inorganic antibacterial agents such as silver supported on activated carbon (JP-A-49-61950) and organic antibacterial and fungicides such as N-' (fluorodichloromethylthio)-phthalimide have been known. . However, the former (inorganic type) has a problem in that silver ions are quickly eluted into the solution and the antibacterial effect cannot be obtained permanently. On the other hand, the latter (organic type) may not show antibacterial activity depending on the type of bacteria (lack of versatility depending on the type of bacteria), and even types with heat resistance
It decomposes or evaporates when kneaded into resin at 300℃,
There were some cases where the effect decreased.

In order to solve the problems of conventional antibacterial agents, so-called antibacterial zeolite, which has antibacterial components supported on zeolite, has been developed (Japanese Patent Publication No. 6122977).
No., Japanese Patent Publication No. 60-181002).

[Problem to be solved by the invention]

The above-mentioned antibacterial zeolite is certainly an excellent antibacterial agent that has excellent antibacterial activity that lasts when left in water or air, and does not change in quality when mixed into resin. However, the antibacterial zeolite has a problem in that it gradually changes color over time. The change in color does not change the antibacterial properties of zeolite, so it remains an antibacterial agent. However, products containing the antibacterial zeolite (for example, products containing the antibacterial zeolite)
The product (molded product) may change color, which may significantly reduce the product value depending on the type of product.

Therefore, the purpose of the present invention is to prevent discoloration over time (
Another object of the present invention is to provide an antibacterial aluminosilicate having antibacterial properties equivalent to those of conventional antibacterial zeolites. Another object of the present invention is to provide a sealing composition containing an antibacterial aluminosilicate that exhibits extremely little discoloration over time.

[Failure to solve the problem]

The present invention provides an antibacterial aluminosilicate in which part or all of the ion-exchangeable ions in the aluminosilicate are replaced with ions of at least one metal selected from the group consisting of alkaline earth metals and manganese and antibacterial metal ions. It concerns acid salts.

The present invention will be explained below.

In the present invention, the aluminosilicate includes zeolite and amorphous aluminosilicate.

Antibacterial zeolite using zeolite as the aluminosilicate will be explained below.

In the present invention, as the "zeolite", both natural zeolite and synthetic zeolite can be used.

Zeolite is generally an aluminosilicate with a three-dimensional skeleton structure, and has the general formula:
2O2'YSi02' ZH20te is displayed. Here, M represents an ion that can be exchanged and is usually 1 or 2.
It is a valent metal ion. n is the valence of the (metal) ion. X and Y represent the respective metal oxide and silica coefficients, and Z represents the number of water of crystallization. Specific examples of zeolites include 8-type zeolide, X-type zeolide, Y-type zeolide, T-type zeolide, high silica zeolite, sodalite, mordenite, analcyme,
Examples include clinoptilolite, chabasite, and erionite. However, it is not limited to these. The ion exchange capacities of these exemplary zeolites are 7 meq/g for 8-type zeolide, 6 meq/g for X-type zeolide, and 4 meq/g for X-type zeolide.
meq/g SY-type zeolide 5 meq/g
ST-type zeolide 3.4 meq/g.

Sodalite 11.5meq/g, Mordenite 2
,6meq/g %Anal Cyme 5meq/g %
Clinoptilolite 2.6 meq/g, Chabasite 5 meq/g, Erionai) 3.8 meq/g
Both have sufficient capacity for ion exchange with ammonium ions and silver ions.

The antibacterial zeolite of the present invention replaces some or all of the ion-exchangeable ions in the zeolite, such as sodium ions, calcium ions, potassium ions, magnesium ions, iron ions, etc. with alkaline earth metals and manganese. It is substituted with at least one kind of metal ion selected from the following and an antibacterial metal ion. Examples of antimicrobial metal ions include ions of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium or thallium, preferably ions of silver, copper or zinc. Further, examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium.

From the viewpoint of antibacterial properties, it is appropriate that the antibacterial metal ions are contained in the zeolite in an amount of 0.1 to 15%.

Antibacterial zeolites containing 0.1-15% silver ions and 0.1-8% copper or zinc ions are more preferred. On the other hand, ions of at least one metal selected from the group consisting of alkaline earth metals and manganese can be contained up to 20% in zeolite, but the content is limited to 3 to 20%.
1696, preferably 5 to 12%, is appropriate from the viewpoint of effectively preventing discoloration of the zeolite. In this specification, % refers to % by weight on a dry basis at 110°C.

The method for producing the antibacterial zeolite of the present invention will be explained below.

The antibacterial zeolite of the present invention is produced by bringing the zeolite into contact with a mixed aqueous solution containing alkaline earth metal and/or manganese ions and antibacterial metal ions prepared in advance, so that the ion-exchangeable ions in the zeolite and the above ions are combined. Replace. The contact is carried out at a temperature of 10-70°C, preferably 40-60°C.
It can be carried out at 0° C. for 3 to 24 hours, preferably for 10 to 24 hours, by a batch method or a continuous method (for example, a column method). It is appropriate to adjust the pH of the above mixed aqueous solution to 3 to 10, preferably 5 to 7. This adjustment is preferable because it can prevent silver oxides and the like from being deposited on the zeolite surface or into the pores. Also, each ion in the mixed aqueous solution is
Both are usually supplied as salt. For example, be IJ IJ
Magnesium ions include beryllium nitrate, beryllium sulfate, etc. Magnesium ions include magnesium nitrate, magnesium sulfate, magnesium thiocyanate, magnesium acetate, etc.
Calcium ions are calcium nitrate, calcium perchlorate, calcium thiosulfate, calcium acetate, etc. Strontium ions are strontium nitrate, strontium acetate, strontium chromate, etc. Barium ions are barium nitrate, etc. Manganese ions are manganese sulfate, perchlorate, etc. Manganese, manganese nitrate, manganese acetate, etc.; silver ions include silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, diammine silver sulfate, etc.; copper ions include copper nitrate (
n), copper perchlorate, copper acetate, potassium tetracyanocuprate, copper sulfate, etc. Zinc ions include zinc nitrate (■), zinc sulfate,
Zinc perchlorate, zinc thiocyanate, zinc acetate, etc., mercury ions include mercury perchlorate, mercury nitrate, mercury acetate, etc., tin ions include tin sulfate, etc., lead ions include lead sulfate, lead nitrate, etc., bismuth ions. are bismuth chloride, bismuth iodide, etc. Cadmium ions are cadmium perchlorate, cadmium sulfate, cadmium nitrate, cadmium acetate, etc. Chromium ions are chromium perchlorate, chromium sulfate, ammonium chromium sulfate, chromium nitrate, etc., thallium ions For example, thallium perchlorate, thallium sulfate, thallium nitrate, thallium acetate, etc. can be used.

The content of alkaline earth metal ions, etc. in the zeolite can be appropriately controlled by adjusting the degree of each ion (salt) in the mixed aqueous solution.

Table 1 shows the relationship between the concentration of alkaline earth metal ions and manganese ions in an aqueous solution and the content in zeolite.
Table 1 also shows the amounts (appropriate amounts and optimal amounts) of each ion suitable for inclusion in the zeolite.

For example, if the antibacterial zeolite contains silver ions, the silver ion concentration in the mixed aqueous solution should be 0.002M/
# ~O, 15Mzl! By doing so, an antibacterial heptaolide having a silver ion content of 0.1 to 5% can be obtained as appropriate. In addition, antibacterial zeolite further contains copper ions,
When containing zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1 M/p to 0.85 M/β, and the zinc ion concentration is 0.15 M/β to 1.2 M/β. , an antibacterial zeolite having a copper ion content of 0.1 to 8% and a zinc ion content of 0.1 to 8% can be obtained.

In the present invention, in addition to the mixed aqueous solution as described above, ion exchange can also be performed by using an aqueous solution containing each ion individually and bringing each aqueous solution into contact with the zeolite sequentially. The concentration of each ion in each aqueous solution can be determined according to the formation of each ion in the mixed aqueous solution.

After ion exchange, the zeolite is thoroughly washed with water and then dried. Drying is preferably carried out at 105° C. to 115° C. under normal pressure or at 70° C. to 90° C. under reduced pressure (1 to 3 Qtorr).

Incidentally, ion exchange of ions without suitable water-soluble salts such as bismuth or organic ions can be carried out using an organic solvent solution such as alcohol or acetone so that hardly soluble basic salts are precipitated.

Next, an antibacterial amorphous aluminosilicate using an amorphous aluminosilicate (hereinafter sometimes referred to as AAS) as the aluminosilicate will be explained.

AAS (amorphous aluminosilicate) used as a raw material in the present invention is not particularly limited, and conventionally known ones can be used as they are.

AAS generally has the composition formula x! , 1.0-A R203・y
It is expressed as Si02.zH20, where M is generally an alkali metal element (eg, sodium, potassium, etc.). Moreover, x and ySz each indicate the molar ratio of metal oxide, silica, and crystal water. Unlike the crystalline aluminosilicate called zeolite, AAS is an amorphous substance that does not show a diffraction pattern even in X-ray diffraction analysis, and the synthesis process produces extremely fine zeolite crystals of several tens of amperes. However, it is thought to have a structure in which an amorphous substance consisting of a complex combination of 5102.AA, 03.M2O, etc. is attached to its surface.

AAS is generally manufactured by adding an aluminum salt solution, a silicon compound solution, and an alkali metal salt solution to a predetermined concentration of 60%.
It is produced by reacting at a low temperature below ℃ and washing with water before crystallization progresses. For example, as a manufacturing method,
There are methods described in No. 58099 and Japanese Patent Application Laid-Open No. 55-162418.

AAS obtained by the above method contains 10% or more of alkali metal oxide. The ΔAS can be used as it is for the production of antibacterial AAS, but setting the M20 content to 10% or less, preferably 8% or less is effective in preventing discoloration of the resin over time when it is converted into resin, etc. It is particularly preferable from the viewpoint of preventing. However, it is not limited to this range.

Further, the antibacterial AΔS of the present invention is ion-exchanged with antibacterial metal ions and ions of at least one metal selected from the group consisting of alkaline earth metals and manganese. Examples of antibacterial metal ions and alkaline earth metal ions include the same ions as those used in the antibacterial zeolite.

Among the antibacterial metals, it is appropriate that the amount of silver converted is 0.1 to 50%, preferably 0.5 to 5%, from the viewpoint of exhibiting excellent antibacterial activity. Furthermore, it is preferable to contain 0.1 to 10% of one or more of copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, and thallium.

Furthermore, at least one metal ion selected from the group consisting of alkaline earth metals and manganese is contained in the AAS in an amount of 25%.
It can be contained up to 3% to 16%, but preferably 3% to 16%
, more preferably 5 to 12%, from the viewpoint of effectively preventing discoloration of the AAS.

The antibacterial AAS can be produced, for example, by the following methods (1) and (2).

m Contacting AAS with an M2C (M is an alkali metal) content of preferably 10% or less and antibacterial metal ions, etc., to exchange the ion-exchangeable ions in AAS with the antibacterial metal ions. Antibacterial AAS can be produced by this method.

(2) Adjust the pH of the AAS slurry to preferably 6 or less, and then bring the AAS in the slurry into contact with antibacterial metal ions to exchange ion-exchangeable ions in AAS with antibacterial metal ions, etc. Antibacterial AAS by
can be manufactured.

In method (1), AAS having an M20 content of preferably 10'% or less is used. The AAS obtained by conventional methods is greater than 10%. Contains M, 0. Therefore, the AAS obtained by the above method is suspended in water, for example, and then an acid aqueous solution is added dropwise to the obtained slurry while stirring to neutralize the alkali metal in the AAS, thereby reducing the M, 0 content to 10. It can be adjusted to below %. 0 as an acid aqueous solution. It is preferable to use a dilute acid aqueous solution having a concentration of IN or less, and to perform the reaction at a dropping rate of 100 mβ/30 minutes or less, although this will vary depending on the stirring conditions and reaction scale.

Furthermore, neutralization is performed until the pH of the slurry is 3 to 6, preferably 4.
It is preferable to set it in the range of 5 to 5. Examples of acids that can be used for neutralization include inorganic acids such as nitric acid, sulfuric acid, perchloric acid, phosphoric acid, and hydrochloric acid, and organic acids such as formic acid, acetic acid, oxalic acid, and citric acid.

The AAS with an M20 content of 10% or less obtained by neutralization can be filtered, washed with water, and used as a slurry in the method (1) as it is, or it can be dried and used as AAS with an M20 content of 10% or less. Good too.

In the method (1), preferably M20 content is 10%
The following slurry of AAS is mixed with an aqueous solution containing antibacterial metal ions and alkaline earth metal ions and/or manganese ions, and AAS is brought into contact with the mixed aqueous solution containing antibacterial metal ions, etc. to exchange ions in AAS. Replace possible ions with the above ions. Contact is 5-70
C., preferably 40 to 60.degree. C., for 1 to 24 hours, preferably 10 to 24 hours, by a batch method or a continuous method (e.g., column method).

Each ion in the mixed aqueous solution is usually supplied as a salt. The salt used can be the same as the salt that can be used in the production of the antibacterial zeolite.

The content of metal ions in AAS can be appropriately controlled by adjusting the degree of each ion (salt) in the mixed aqueous solution. For example, when the antibacterial AAS contains silver ions, the silver ion concentration in the mixed aqueous solution is set to 0.01.
By setting M/7 to 0.30 M/l, an antibacterial AAS having an appropriate silver ion content of 0.5 to 6% can be obtained. Further, when the antibacterial AAS further contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.05 M/l to 0.4 M/ji! By setting the zinc ion concentration to 0 and '05M/1 to 0.4M/1, antibacterial AAS with a copper ion content of 1 to 8% and a zinc ion content of 1 to 8% can be obtained as appropriate. .

In addition to the mixed aqueous solution as described above, ion exchange can also be carried out by using an aqueous solution containing each ion individually and bringing each aqueous solution into contact with AAS sequentially. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.

After ion exchange, the AAS is thoroughly washed with water and then dried. Drying is preferably carried out at 105°C to 115°C under normal pressure or 70°C to 90°C under reduced pressure (1 to 30 Torr).

Incidentally, ion exchange of ions without suitable water-soluble salts such as tin and bismuth can be carried out using an organic solvent solution such as alcohol or acetone so that hardly soluble basic salts are precipitated.

On the other hand, in method (2), the pH of the AAS slurry obtained by a conventional method is adjusted to 6 or less, preferably 3 to 6, more preferably 4 to 5, and the M20 content in AAS is reduced to 10%.
It can be as follows. For adjusting the pH, the method exemplified in the method (1) above can be used similarly.

The AAS in the slurry can then be ion-exchanged by mixing the p++-adjusted slurry with a solution containing antibacterial metal ions and alkaline earth metal ions and/or manganese ions. As the ion exchange method, a method similar to method (1) can be used as is.

The antibacterial aluminosilicate of the present invention also includes those containing ammonium ions through ion exchange in addition to the antibacterial metal ions and the like.

The present invention also provides an antibacterial resin composition containing the above antibacterial aluminosilicate and resin. +M fingers include, for example, polyethylene, polypropylene, vinyl chloride, AB
S resin, nylon, polyester, polyvinylidene chloride, polyamide, polystyrene, polyacetal, polyvinyl alcohol, polycarbonate, acrylic resin,
Thermoplastic or thermosetting materials such as fluororesin, polyurethane elastomer, polyester elastomer, phenolic resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, urethane resin, rayon, cupro, acetate, triacetate, vinylidene, natural and synthetic rubber, etc. The antibacterial (grease-proof) composition of the present invention can be obtained by directly injecting the antibacterial aluminosilicate into the resin or by coating the surface of the resin. From the viewpoint of adding antibacterial, anti-mold, and anti-algae functions, it is appropriate to contain 0.05 to 80%, preferably 0.1 to 80%, of antibacterial aluminosilicate. From the point of view of prevention, the content of antibacterial aluminosilicate should be reduced to 0.
It is preferably 1 to 3%.

The antibacterial aluminosilicate of the present invention can be used in various fields.

In the aquatic field, it can be used as an antibacterial and antialgal agent for water purifiers, cooling tower water, and various types of cooling water, and can also be used as a cut flower life extension agent.

In the paint field, oil-based paints, lacquers, varnishes, A/L/+
It can be directly mixed with various paints such as resin-based, aminoalkyd-based, vinyl resin-based, acrylic resin-based, epoxy resin-based, urethane resin-based, water-based, powder-based, chlorinated rubber-based, phenol-based, etc., or applied to the surface of the coating film. It is possible to add antibacterial, anti-mold, and anti-algae functions to the paint film by coating it. In the construction field, it can be mixed with joint materials, wall materials, tiles, etc., or coated on their surfaces to add antibacterial, anti-mold, and anti-algae functions.

In the paper manufacturing field, it is possible to add antibacterial and antifungal functions to wet tissues, paper packaging materials, cardboard, paper, and freshness-preserving paper by incorporating or coating them. It can also be used as a slime control agent in the field.

The antibacterial aluminosilicate of the present invention can be used not only in the above-mentioned fields but also in all fields that require prevention of the generation and proliferation of microorganisms such as general bacteria, fungi, and algae.

Furthermore, the antibacterial aluminosilicate of the present invention has been disclosed in Japanese Patent Application No. 62
It can also be used as an antibacterial powder for a dispersion as disclosed in Japanese Patent No. 331112.

The present invention will be explained in more detail below with reference to Examples.

Example 1 (Preparation method of antibacterial aluminosilicate) Aluminosilicate is A-type zeolite (Na20・Aβ203'
1.9S102・XLO: Average particle size 1.5/-! m
),' X-type zeolite (Na20・8j2203
・2.3SiO, ・XH2O; average particle size 2.5 μm),
Y-type zeolite (1,1Na20 ・A j! 20
3'4S102'XLO; average particle size 0.7 μm
), natural mordenite (150-250 mesh) and amorphous aluminosilicate (0,93Na, O'A
N2L'2.55S102; average particle size 0.3 μm
) were used. As salts to provide each ion for ion exchange, NH, NO3, 8gNo,
, Zn(No3)2, Be(NOi)z, Mg(No
3) 2, (:u (NO3) 2, Sr (NO3)
2, Ba (NO3) 2 and Mn (NO,) 2 were used.

Tables 2-1 and 2-2 show the type of aluminosilicate used in preparing each sample and the type and concentration of salt contained in the mixed aqueous solution. Nα0 to Nα8 and Nα10 to Nα1
Seventeen types of antibacterial aluminosilicate samples were obtained.

For each sample, water was added to 1 kg of aluminosilicate powder heated and dried at 110°C to make a 1.3β slurry, then stirred and degassed, and an appropriate amount of 0.5N nitric acid solution and water were added. Adjust the pH to 5-7 and bring the total volume to 1.8.
It was made into a slurry of fl. Next, for ion exchange, a mixed aqueous solution 31 of a specified salt at a specified concentration was added to bring the total volume to 4.8 I.
1, and this slurry liquid was maintained at 40 to 60°C and heated to 10 to
The mixture was kept stirring for 24 hours to reach an equilibrium state. After the ion exchange was completed, the aluminosilicate sarcophagus was washed with room temperature water or warm water until excess silver ions in the aluminosilicate phase were removed. Next, the samples were heated and dried at 110° C. to obtain 17 types of samples. Data regarding the antibacterial aluminum nosilicate samples obtained are shown in Tables 2-1 and 2-2.

Example 2 (antibacterial activity test) The antibacterial activity was evaluated by the following method.

The test strain was Aspergillus niger (Aaper
gillus niger) [Fo 4407 (
mold), Candita albicans (Candida
alb+cans) IFO1594 (yeast), Pseudomonas aeruginosa
Three types of bacteria were used: S. eruginosa) 110 P-1 (common bacteria).

Enrichment medium for bacteria: Mueller-Hinton
Broth (Difco), For mold: Potato dextrose agar medium (Eiken), For yeast: Yeast Mo
rphology Agar (Difco) was used. Susceptibility measurement medium for bacteria: Mueller-Hin
ton Medium (Difco) and Sabouraud agar medium (Eiken) for mold and yeast were used.

A plate for sensitivity measurement was prepared as follows.

Prepare a diluted suspension of each sample with sterile purified water, and add this to a susceptibility measurement medium at 50 to 60°C after dissolution.
Add 1/9 cup of the culture medium, mix thoroughly, then dispense into a petri dish.
It was solidified to form a flat plate for sensitivity measurement.

Preparation of bacterial solution for inoculation was for bacteria: A test bacterial strain that had been subcultured was inoculated into an enrichment medium, and diluted with an enrichment medium so that the idle number after culture was 106/mβ to prepare a bacterial solution for inoculation.

For molds: Inoculate the subcultured test bacterial strain into an enrichment medium, suspend the conidia formed after culturing in a sterile 0.05% polysorbate 80 solution to a ratio of approximately 10'/n+j2, and mix with the inoculating bacterial solution. did. For yeast: An enrichment medium was inoculated with a subcultured test strain, and the cells formed after culturing were suspended in sterilized physiological saline to a concentration of approximately 106/mβ to obtain an inoculum solution.

The culture was carried out as follows.

The bacterial solution for inoculation was smeared with a nichrome wire loop (approximately 1 mm in inner diameter) on a plate for susceptibility measurement in a 2 cm line, and the bacteria was heated at 37°C.
, 18-20 hours, and the mold was incubated at 25°C for 7 days. The concentration at which growth was inhibited after culturing for a predetermined period of time was determined as the minimum inhibitory concentration.

The results obtained are shown in Table 3.

Example 3 (Discoloration test) The antibacterial aluminosilicate obtained in Example 1 was heated and dried, and then kneaded into polypropylene (polypropylene: J-109G manufactured by Ube Industries) at a concentration of 11 wt%, and then injection molded (retention). Time: 2 minutes) to obtain a sample (piece size: 7.3c
m x 4.4 cm x 2 mm). The obtained sample was exposed to sunlight outdoors. The color of the samples is determined by printing each sample on white ketone paper (L*a"b"93.1, -0, 7, -0
．． 5) and measured using a Minolta color difference meter CR-100 model (using D65 light beam). CIF 19
76, the ratio of sample L* expressed in the L*a*b* color system to blank L* is calculated and the results are shown in Figures 1~
It is shown in Figure 4.

〔Effect of the invention〕

The antibacterial aluminosilicate of the present invention has antibacterial activity equivalent to that of conventional antibacterial zeolite, and has much less color change over time than conventional products, and is a further improvement over conventional products. . (See Figures 1 to 4)

[Brief explanation of the drawing]

Figures 1 to 4 show the color change over time of polypropylene samples mixed with antibacterial aluminosilicate. Figure 1: Number of days elapsed Figure 2: Number of days elapsed Figure 3: Number of days elapsed

Claims (4)

[Claims] (1) Antibacterial aluminosilicate in which part or all of the ion-exchangeable ions in the aluminosilicate are replaced with at least one metal ion selected from the group consisting of alkaline earth metals and manganese and antibacterial metal ions. . (2) The antibacterial agent according to claim (1), wherein the antibacterial metal ion is an ion of at least one metal selected from the group consisting of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, and thallium. aluminosilicate. (3) The antibacterial aluminosilicate according to claim (1), wherein the aluminosilicate is a zeolite or an amorphous aluminosilicate. (4) An antibacterial resin composition comprising the antibacterial aluminosilicate according to claim (1) and a resin.