JP2598961B2 - Antibacterial aluminosilicate - Google Patents

Description

Description: TECHNICAL FIELD 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 discolor over time. The present invention relates to an acid salt and an antibacterial resin composition.

[Conventional technology]

Conventionally, an inorganic antibacterial agent, for example, silver supported on activated carbon (JP-A-49-61950), and an organic antibacterial fungicide, for example, N- (fluorodichloromethylthio)-
Phthalimides are known. However, the former (inorganic type) has a problem that silver ions are quickly eluted into a solution and an antibacterial effect cannot be obtained permanently. On the other hand, the latter (organic type) does not exhibit antibacterial action depending on the type of bacteria (lack of versatility depending on the type of bacteria), and even the type with heat resistance is 150-300 ° C. In some cases, it is decomposed or evaporated when kneaded into the resin, and the effect is reduced.

In order to solve such problems of the conventional antibacterial agents, a so-called antibacterial zeolite in which an antibacterial component is supported on zeolite has been developed (Japanese Patent Publication No. 22977/1986).
No., JP-A-60-181002).

[Problems to be solved by the invention]

The above-mentioned antibacterial zeolite is an excellent antibacterial agent which has excellent antibacterial activity when left in water or air, and does not deteriorate when kneaded into a resin. However, there has been a problem that the antibacterial zeolite gradually changes its color over time. The discoloration does not change the antimicrobial properties of the zeolite, and therefore remains excellent as an antimicrobial agent. However, a product to which the antibacterial zeolite is added (for example, a resin molded article containing the antibacterial zeolite) may be discolored, and depending on the type of the product, the commercial value may be significantly reduced.

Therefore, an object of the present invention is to provide an antibacterial aluminosilicate that does not discolor over time and has excellent antibacterial properties equivalent to conventional antibacterial zeolites. Another object of the present invention is to provide a resin composition containing an antibacterial aluminosilicate that has extremely little discoloration with time.

[Means for solving the problem]

The present invention relates to an antibacterial aluminosilicate in which part or all of ion-exchangeable ions in the aluminosilicate are replaced with at least one kind of amine ion and an antibacterial metal ion.

 Hereinafter, the present invention will be described.

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

Hereinafter, an antibacterial zeolite using zeolite as an aluminosilicate will be described.

In the present invention, as the “zeolite”, both natural zeolites and synthetic zeolites can be used. Zeolite is generally an aluminosilicate having a three-dimensional skeleton structure, and has a general formula of XM _{2 / n} O.Al ₂ O _3.
Displayed as YSiO ₂ · ZH ₂ O. Here, M represents an ion-exchangeable ion and is usually a monovalent or divalent metal ion. n is the valence of the (metal) ion. X and Y indicate the respective metal oxides and silica coefficients, and Z indicates the number of crystal waters. Specific examples of zeolite include, for example, A-
Type zeolite, X-type zeolite, Y-type zeolite,
Examples include T-type zeolites, high silica zeolites, sodalite, mordenite, analcyme, clinoptilolite, chabazite, erionite, and the like. However, it is not limited to these. The ion exchange capacity of these exemplified zeolites is 7 m of A-type zeolite.
eq / g, X-type zeolite 6.4meq / g, Y-type zeolite 5m
eq / g, T-type zeolite 3.4meq / g, sodalite 11.5me
q / g, mordenite 2.6meq / g, analcyme 5meq / g, clinoptilolite 2.6meq / g, chabazite 5meq / g, erionite 3.8meq / g, all of which are ion-exchanged with ammonium ions and silver ions. Has sufficient capacity.

The antibacterial zeolite of the present invention is an ion-exchangeable ion in the zeolite, for example, sodium ion, calcium ion, potassium ion, magnesium ion,
Part or all of iron ions and the like are replaced with at least one kind of amine ions and antibacterial metal ions. Examples of antimicrobial metal ions include silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium or thallium ions, preferably silver, copper or zinc ions. The amine ions include primary amine (RNH ₂ ) ions, secondary amine (R ₂ NH) ions,
Tertiary amine (R ₃ N) ions and quaternary ammonium (R ₄ N
⁺ ) Ions. R represents a hydrocarbon group, and the hydrocarbon group is an aliphatic hydrocarbon group [linear or branched alkyl group (for example, having 1 to 16, preferably 1 to 11, more preferably 1 to 5 carbon atoms). Alkyl group), the alkyl group may have a substituent (eg, a carboxyl group, a hydroxyl group, etc.), an unsaturated aliphatic group, an alicyclic group (eg, a cycloalkyl group having 3 to 6 carbon atoms)] And an aromatic hydrocarbon group which may have a substituent.
Each R in R ₂ NH, R ₃ N and R ₄ N ⁺ may be the same or different. Specific examples of the amine include aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, and cetylamine; dimethylamine, diethylamine, dipropylamine, and diisopropylamine. Aliphatic secondary amines such as amine, dibutylamine and diamylamine; trimethylamine;
Aliphatic tertiary amines such as triethylamine, tripropylamine, tributylamine and triamylamine; aliphatic unsaturated amines such as allylamine, diallylamine and triallylamine; alicycles such as cyclopropylamine, cyclobutylamine, cyclopentylamine and cyclohexylamine Formula amines; and aromatic amines such as aniline, methylaniline, ethylaniline, diethylaniline, toluidine, benzylamine, diphenylamine, and naphthylamine.

From the viewpoint of antibacterial properties, it is appropriate that the above antibacterial metal ions are contained in the zeolite in an amount of 0.1 to 15%. 0.1 to 15% of silver ion and 0.1 to 8 of copper or zinc ion
% Is more preferable. On the other hand, at least one amine ion can be contained in the zeolite up to 20%, but the content is 0.5 to 15%,
Preferably, the content is 0.5 to 5% from the viewpoint of effectively preventing discoloration of the zeolite. In addition, in this specification,% means weight% of 110 degreeC dry basis.

Hereinafter, the method for producing the antibacterial zeolite of the present invention will be described.

The antibacterial zeolite of the present invention is prepared by bringing a zeolite into contact with a mixed aqueous solution containing an amine ion and an antibacterial metal ion prepared in advance, and replacing the ion-exchangeable ion in the zeolite with the above ion. Contact is 10-70
C., preferably at 40-60 ° C. for 3-24 hours, preferably 10-
It can be performed by a 24-hour batch system or a continuous system (for example, a column method). The pH of the mixed aqueous solution is suitably adjusted to 3 to 10, preferably 5 to 7. This adjustment is preferable because it is possible to prevent the silver oxide or the like from extending to the zeolite surface or into the pores. Each ion in the mixed aqueous solution is usually supplied as a salt. For example, silver ion is silver nitrate, silver sulfate, silver perchlorate, silver acetate, silver diammine nitrate, silver diamine silver sulfate, and copper ion is copper (II) nitrate, copper perchlorate, copper acetate, potassium tetracyanocuprate, Copper sulfate etc., zinc ion is zinc nitrate (II), zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate etc. Mercury ion is mercury perchlorate, mercury nitrate, mercury acetate etc., tin ion is sulfuric acid Lead ions such as tin, lead sulfate, lead nitrate, etc.
Bismuth ions include 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., and thallium ions are thallium perchlorate, thallium sulfate, Thallium nitrate, thallium acetate and the like can be used.

The content of amine ions and the like in the zeolite can be adjusted by adjusting the concentration of each ion (salt) in the mixed aqueous solution.
It can be controlled appropriately. By setting the concentration of the amine ion in the aqueous solution to 0.1 to 1.0 M /, the content of the amine in the zeolite can be set to 0.05 to 0.6%.

Further, for example, when the antibacterial zeolite contains silver ions, the silver ion concentration in the mixed aqueous solution is 0.002 M / ~
By setting it to 0.15 M /, the silver ion content is appropriately set to 0.1.
1-5% of antimicrobial zeolites can be obtained. or,
When the antibacterial zeolite further contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1 M /
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 appropriately obtained by setting the zinc ion concentration to 0.15M / -1.2M / and the zinc ion concentration to 0.15M / -1.2M /.

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

The zeolite after the ion exchange is thoroughly washed with water and then dried. Drying is preferably performed at 105 ° C. to 115 ° C. under normal pressure, or at 70 ° C. to 90 ° C. under reduced pressure (1 to 30 torr).

In addition, ion-exchange of ions or organic ions without suitable water-soluble salts such as tin and bismuth can be carried out using an organic solvent solution such as alcohol and acetone so as to prevent hardly soluble basic salts from being extracted. .

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

AAS (amorphous aluminosilicate) used as a raw material in the present invention is not particularly limited, and a conventionally known one can be used as it is. AAS generally has the composition formula xM ₂ O
· Al ₂ O ₃ · ySiO appear in ₂ · zH ₂ O, where M is typically an alkali metal element (such as sodium, potassium, etc.). In addition, x, y, and z indicate the molar ratios of metal oxide, silica, and water of crystallization, respectively. Unlike crystalline aluminosilicate, which is called zeolite, AAS is an amorphous substance that does not show a diffraction pattern even in X-ray diffraction analysis, and produces extremely fine zeolite crystals of several tens of amps in the synthesis process. However, it is considered to have a structure in which an amorphous substance in which SiO ₂ , Al ₂ O ₃ , M ₂ O, and the like are combined in a complex manner adheres to the surface thereof. AAS is generally produced by reacting an aluminum salt solution, a silicon compound solution, and an alkali metal salt solution at a predetermined concentration in a low temperature range of 60 ° C. or lower, and washing with water before crystallization proceeds. Examples of the production method include those described in JP-B-52-58099 and JP-A-55-162418.

AAS obtained by the above method has 1 alkali metal oxide.
0% or more is contained. The AAS can be used as it is for the production of antibacterial AAS, but has an M ₂ O content of 10% or less,
It is particularly preferable that the content be 8% or less, from the viewpoint of effectively preventing time-dependent discoloration of the resin or the like when converted into the resin or the like. However, it is not limited to this range.

Further, the antibacterial AAS of the present invention has been ion-exchanged with antibacterial metal ions and at least one amine ion. Examples of the antibacterial metal ion and the amine ion include the same ions as those used for the antibacterial zeolite.

The amount of silver added to the antibacterial metal is 0.1 to 50%, preferably 0.5 to 5%, from the viewpoint of exhibiting excellent antibacterial activity. In addition, copper, zinc, mercury, tin,
It is preferable to contain 0.1 to 10% of any one or more metals of lead, bismuth, cadmium, chromium and thallium.

Also, at least one type of amine ion is 15% in AAS.
, But preferably 0.5 to 8
%, More preferably 0.5 to 2%, 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).

(1) An AAS having a content of M ₂ O (M is an alkali metal) of preferably 10% or less is brought into contact with an antibacterial metal ion or the like, so that an ion-exchangeable ion and the antibacterial metal ion in the AAS are exchanged. By exchanging, an antibacterial AAS can be manufactured.

(2) Adjusting the pH of the AAS slurry to preferably 6 or less, and then bringing the AAS in the slurry into contact with antibacterial metal ions to exchange the ion-exchangeable ions in AAS with antibacterial metal ions and the like. By doing so, an antibacterial AAS can be produced.

In the method (1), AAS having a M ₂ O content of preferably 10% or less is used. AA obtained in the usual way
S exceeds 10%. Contains M ₂ O. Therefore, by suspending the AAS obtained by the above method in water, for example, and then dropping an aqueous acid solution while stirring the obtained slurry.
Neutralize alkali metals in AAS to reduce M ₂ O content
It can be adjusted to 10% or less. 0.1N as acid aqueous solution
It is preferable to use a dilute acid aqueous solution having the following concentration, and to carry out the reaction at a dropping rate of 100 ml to 30 minutes or less, depending on the stirring conditions and reaction scale. Furthermore, neutralization is performed when the pH of the slurry is 3 to 6,
Preferably, it is in the range of 4 to 5. Examples of the acid 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.

AAS with an M ₂ O content of 10% or less obtained by neutralization is filtered,
After washing with water, the slurry can be used as it is in the method (1), or it can be dried to form AAS having an M ₂ O content of 10% or less.

In the method (1), preferably, a slurry of AAS having an M ₂ O content of 10% or less and an aqueous solution containing antibacterial metal ions and amine ions are mixed, and AAS is contacted with a mixed aqueous solution containing antibacterial metal ions and the like. Then, the ion-exchangeable ions in the AAS are replaced with the above-mentioned ions. Contact is 5
70 ° C., preferably 40 to 60 ° C. for 1 to 24 hours, preferably 10
It can be performed by a batch system or a continuous system (for example, a column method) for up to 24 hours.

Each ion in the mixed aqueous solution is usually supplied as a salt. As the salt to be used, the same salts as those used in the production of the antibacterial zeolite can be used.

The content of amine and metal ion in AAS is adjusted by adjusting the concentration of each ion (salt) in the mixed aqueous solution.
It can be controlled appropriately. For example, the content of the amine in the antibacterial AAS is 0.1 to 1 M /
By doing so, it can be 0.08 to 0.8%. When the antibacterial AAS contains silver ions, the silver ion concentration in the mixed aqueous solution is adjusted to 0.01 M // 0.30 M / to appropriately control the antibacterial AAS having a silver ion content of 0.5〜6%.
Obtainable. In addition, antibacterial AAS is more copper ion,
When containing zinc ions, the copper ion concentration in the mixed aqueous solution is 0.05M / ~ 0.4M /, the zinc ion concentration is 0.05M /
By setting it to 0.4 M /, an antibacterial AAS having a copper ion content of 1 to 8% and a zinc ion content of 1 to 8% can be obtained as appropriate.

Ion exchange can also be performed by using an aqueous solution containing each ion alone in addition to the mixed aqueous solution as described above and sequentially contacting each aqueous solution with AAS. The concentration of each ion in each aqueous solution can be determined according to each ion concentration in the mixed aqueous solution.

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

The 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 do not precipitate.

On the other hand, in the 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 M ₂ O content in the AAS is adjusted to 10%. % Or less. For the adjustment of the pH, the method exemplified in the method (1) can be used similarly.

Then, the pH-adjusted slurry was mixed with a solution containing an antibacterial metal ion and an amine ion, and AA in the slurry was mixed.
S can be ion-exchanged. As the ion exchange method or the like, the same method as the method (1) can be used as it is.

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

The present invention also provides an antibacterial resin composition containing the above antibacterial aluminosilicate and a resin. As the resin, for example, polyethylene, polypropylene, vinyl chloride resin,
ABS resin, polyester, polyvinylidene chloride, polyamide, polystyrene, polyacetal, polyvinyl alcohol, polycarbonate, acrylic resin, fluorine resin, polyurethane elastomer, polyester elastomer, phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, Urethane resin,
Examples include thermoplastic or thermosetting resins such as rayon, cupra, acetate, natural and synthetic rubbers.
The antimicrobial resin composition of the present invention can be obtained by directly kneading the antimicrobial aluminosilicate into the resin or coating the resin on the surface. From the viewpoint of adding antibacterial, antifungal and antialgal functions to the above resin, it is suitable to contain 0.05 to 80%, preferably 0.1 to 80% of an antibacterial aluminosilicate. From the viewpoint of substantially preventing discoloration of the resin, the content of the antibacterial aluminosilicate is 0.1%.
It is preferable to set it to ３3%.

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

In the water system field, it can be used as a germicidal and algicidal agent for water purifiers, cooling tower water, and various types of cooling water, and can also be used as a cut flower prolonging agent.

In the field of paints, oil paints, lacquers, varnishes, alkyl resin types, amino alkyd resin types, vinyl resin types, acrylic resin types, epoxy resin types, urethane resin types, aqueous types,
It is possible to add antibacterial, antifungal and anti-algal functions to the paint film by directly mixing it with various paints such as powder, chlorinated rubber and phenol paints or coating it on the surface of the paint film. In the field of construction, it is possible to add antibacterial, antifungal and antialgal functions by mixing with joint materials, wall materials, tiles, and the like, or coating them.

Wet tissue, paper packaging, cardboard,
It is possible to add an antibacterial and antifungal function to these papers by making or coating them on a sheet of paper or freshness-keeping paper, and it can also be used as a slime control agent especially in the papermaking field.

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

Further, the antibacterial aluminosilicate of the present invention is disclosed in Japanese Patent Application
-331112 can also be used as an antibacterial powder for a dispersion.

 Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 (Preparation method of antibacterial aluminosilicate) Aluminosilicate is an A-type zeolite (Na ₂ O.Al ₂ O ₃
· 1.9SiO ₂ · XH ₂ O; average particle size 1.5 [mu] m), X-type zeolite _{(Na 2 O · Al 2 O} 3 · 2.3SiO 2 · XH 2 O; average particle size 2.5 [mu] m), Y
Zeolite (1.1Na ₂ O ・ Al ₂ O ₃・ 4SiO ₂・ XH ₂ O; average particle size
0.7 μm), natural mordenite (150-250 mesh) and amorphous aluminosilicate (0.93Na ₂ O.Al ₂ O ₃ .2.55SiO
₂ ; average particle diameter: 0.3 μm). AgNO is used as a compound to provide each ion for ion exchange.
_3. Seven types were used: methylamine, dimethylamine, trimethylamine, allylamine, aniline sulfate and cycle propylamine.

Table 1 shows the types of aluminosilicate used in preparing each sample and the types and concentrations of the compounds contained in the mixed aqueous solution. Samples of 13 kinds of antibacterial aluminosilicates No. 1 to No. 13 were obtained.

In each sample, 1 kg of aluminosilicate powder heated and dried at 110 ° C. was mixed with water to form a slurry of 1.3, then stirred and degassed, and further added with an appropriate amount of 0.5 N nitric acid solution and water to adjust the pH to 5. Adjusted to ~ 7 to give a total volume of 1.8 slurry. Next, for ion exchange, a mixed aqueous solution 3 of a predetermined compound having a predetermined concentration was added to make the total volume 4.8, and the slurry was kept at 40 to 60 ° C. and stirred for 10 to 24 hours to reach an equilibrium state. Held. After completion of the ion exchange, the aluminosilicate phase was filtered and washed with water at room temperature or warm water until excess silver ions in the aluminosilicate phase disappeared. Next, the sample was dried by heating at 110 ° C. to obtain 13 types of samples. Table 1 shows data on the obtained antibacterial aluminosilicate samples.

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

Test strains include Aspergillus niger (Aapergil
lus niger) IFO4407 (mold), Candida albicans (Candida albicans) IFO1594 (yeast), Pseudomonas aeruginosa IID P
-1 (general bacteria) was used.

Enrichment medium is for bacteria: Mueller-Hinton Broth (Difc
o), for mold: Potato dextrose agar medium (Eiken), for yeast: Yeast Morphology Agar (Difco). Sensitivity measurement medium for bacteria: Mueller-Hinton Med
ium (Difco) for mold and yeast: Sabouraud agar medium (Eiken) was used.

 Preparation of a sensitivity measurement plate was performed as follows.

Prepare dilution suspensions of each sample in sterile purified water,
This was added to a medium for sensitivity measurement at 50 to 60 ° C. after dissolution, and 1/9 of the medium was added. After sufficient mixing, the mixture was dispensed into a petri dish and solidified to obtain a plate for sensitivity measurement.

Preparation of inoculum for bacterial use: For bacteria: Inoculate the enrichment medium with the subcultured test strain, dilute with the enrichment medium so that the number of bacteria becomes 10 ⁶ / ml after culturing, and mix did.

For molds: Inoculate a test strain that has been subcultured into a culture medium for enrichment,
Sterilize the conidia formed after culture to about 10 ⁶ / ml 0.05
% Polysorbate 80 solution to give a bacterial solution for inoculation. For yeast: A test strain subcultured was inoculated into a culture medium for enrichment, and the cells formed after the culture were suspended in sterile physiological saline at a concentration of about 10 ⁶ / ml to obtain an inoculated bacterial solution.

 The culture was performed as follows.

Bacterial solution for inoculation is smeared on a plate for sensitivity measurement with a nichrome wire loop (inner diameter about 1 mm) for about 2 cm.
The mold was cultured for 7 hours at 25 ° C. for 20 hours. The minimum growth inhibitory concentration was determined as the concentration at which growth was inhibited after culturing for a predetermined time.

 Table 2 shows the obtained results.

Example 3 (Discoloration test) The antibacterial aluminosilicate obtained in Example 1 was heated and dried, kneaded into a resin (polypropylene: J-109G manufactured by Ube Industries, Ltd.) at a kneading amount of 1 wt%, and then injection molded (residence time). 2 minutes)
(Piece size: 7.3cm × 4.4cm × 2m
m). The obtained sample was irradiated with sunlight outdoors. The color of each sample was determined by converting each sample to white ketone paper (L ^* a ^* b ^* 9).
3.1, -0.7, -0.5) on the Minolta colorimeter CR
It was measured using a -100 type (using a _D65 light beam). CIF 1976
The ratio of L ^* to the blank L ^* of the sample represented by the L ^* a ^* b ^* color system was determined, and the results are shown in FIGS. 1 to 4.

〔The invention's effect〕

The antibacterial aluminosilicate of the present invention has an antibacterial activity equivalent to that of the conventional antibacterial zeolite, and has a far less change in color over time than the conventional product, and is a further improvement of the conventional product. . (See FIGS. 1-4).

[Brief description of the drawings]

FIG. 1 to FIG. 4 show the change over time of the color of a resin (polypropylene) sample into which an antibacterial aluminosilicate has been kneaded.

 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Koji Sugiura 1489-10 Sasahara, Nozomi, Tenjiro-cho, Tenpaku-cho, Nagoya-shi, Aichi (56) References JP-A-62-20541 (JP, A) JP-A-60-160 181002 (JP, A) JP-A-62-27748 (JP, A) JP-B-61-22977 (JP, B2)

Claims (3)

(57) [Claims] An antibacterial aluminosilicate in which part or all of the ion-exchangeable ions in the aluminosilicate are replaced with silver ions and at least one amine ion. 2. The antibacterial aluminosilicate according to claim 1, wherein the aluminosilicate is zeolite or amorphous aluminosilicate. 3. An antimicrobial resin composition containing the antimicrobial aluminosilicate according to claim 1 or 2.