KR100949719B1 - Antibacterial zeolite resin composition - Google Patents

Abstract

PURPOSE: An anti-bacterial zeolite resin composition is provided to enhance anti-bacterial activity of the resin and prevent decoloration by performing surface treatment on the zeolite with a specific organic compound(PIBSA). CONSTITUTION: An anti-bacterial zeolite resin composition is prepared by performing surface treatment of anti-bacterial zeolite of chemical formula I, Xm2/No Al2O3 ySiO2 zH2O with Poly Isobutylene Succinic Anhydride(PIBSA) which is an organic compound of chemical formula II. In chemical formula I, M is zinc, copper and silver ion. The content of silver ion, copper ion, and zinc ion is 0.1-10 weight%, 0.1-15 weight%, and 0.1-20 weight%.

Description

Antibacterial Zeolite Resin Composition

The present invention relates to an antimicrobial composition and an antimicrobial resin composition containing the antimicrobial composition, which is excellent in dispersibility in processing with resin, extremely little discoloration and deterioration of the resin, and exhibits stable antimicrobial activity over a long period of time. .

Conventionally, metal ions such as zinc, copper and silver ions have been known to exhibit antimicrobial activity. In addition, many studies have been conducted to utilize the antimicrobial activity of these antimicrobial metal ions stably and continuously. Among them, inorganic antimicrobial agents that carry these antimicrobial ions on inorganic carriers are continuously attracting attention.

Inorganic antimicrobial agent is a metal carrier such as zinc, copper and silver ions that exhibit antimicrobial properties. It is supported by the ion exchange reaction of zeolite, which is a carrier with excellent ion exchange ability. It is mixed to provide a resin endowed with antimicrobial activity.

However, when these antimicrobial agents are added to the resin, compatibility with the resin is greatly reduced, resulting in a phenomenon in which the antimicrobial zeolite aggregates locally, resulting in a decrease in the antimicrobial activity of the resin and the inability to reproduce the antimicrobial power. As a result, a larger amount of antimicrobial agent is incorporated into the resin in order to enhance the antibacterial activity, which causes another problem such as discoloration of the resin, deterioration of physical properties, and cost increase.

In order to solve this problem, Korean Patent Registration 10-0482298 provides an antimicrobial zeolite composition prepared by surface treatment with an organometallic compound represented by the following formula (III), and an antimicrobial resin composition prepared using the composition.

Equation III

(R ₁ O) 4-nSiR ₂ n

Wherein R ₁ is an alkyl group having 1 to 15 carbon atoms, an alkoxyalkyl group, R ₂ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, a hydroxyalkyl group, alkoxy Alkyl group, aminoalkyl group, alkylaminoalkyl group, n is an integer or fraction in the range of 0≤n≤3.

However, even with this method, it is difficult to achieve a complete improvement of discoloration problem and dispersibility, and in particular, there is a disadvantage in that additional cost and long time are required due to the surface treatment.

The present invention is to solve the problem to provide an antimicrobial resin composition excellent in dispersibility in processing with resin, very little discoloration and deterioration of the resin, and exhibiting stable antimicrobial activity over a long period of time.

In order to solve the above problems, the present invention proposes a surface treatment of a zeolite substituted with an antimicrobial metal ion with an organic compound represented by a specific molecular formula (PIBSA) as a main means for solving the problems.

More specifically, the present invention provides an antimicrobial zeolite of formula (I) substituted with at least one metal ion selected from zinc, copper, silver, mercury, tin, lead, bismuth, cadmium, chromium and thallium ions It provides an antimicrobial resin composition prepared by surface treatment with an organic compound (Poly Isobutylene Succinic Anhydride or less PIBSA) represented by.

[Formula I]

xM ₂ / nO Al ₂ O ₃ ySiO ₂ zH ₂ O

In the formula, M represents an ion exchangeable metal ion and generally represents monovalent or divalent alkali or alkaline earth metal ions, n represents the valence of the ion, x and y represent the coefficients of the metal oxide and silica, respectively. z represents the number of crystallized water.

[Formula II]

The antimicrobial resin composition according to the present invention is excellent in the dispersibility of the antimicrobial agent, not only discoloration and deterioration of the resin, but also has the effect of exhibiting stable antimicrobial activity over a long period of time.

The present invention is represented by the following formula (II) to the antimicrobial zeolite of formula (I) substituted with at least one metal ion selected from zinc, copper, silver, mercury, tin, lead, bismuth, cadmium, chromium and thallium ions. The present invention relates to an antimicrobial zeolite composition obtained by surface treatment with an organic compound (PIBSA), and an antimicrobial resin composition prepared using the composition.

[Formula I]

xM ₂ / nO Al ₂ O ₃ ySiO ₂ zH ₂ O

In the formula, M represents an ion exchangeable metal ion and generally represents monovalent or divalent alkali or alkaline earth metal ions, n represents the valence of the ion, x and y represent the coefficients of the metal oxide and silica, respectively. z represents the number of crystallized water.

Examples of such zeolites include A-type zeolites, X-type zeolites, Y-type zeolites, high silica zeolites, soulite, mordenite, analnitite, clinoptilolite, cavirite and eninonitite.

Zeolite ion-exchangeable metal ions are antimicrobial metal ions including at least one metal ion selected from zinc, copper, silver, mercury, tin, lead, bismuth, cadmium, chromium and thallium ions. Preferably, zinc, copper and silver ions are used.

The content of metal ions is in the range of 0.1 to 10% by weight relative to the weight of the zeolite, the content of copper ions in the range of 0.1 to 15% by weight, and the content of zinc ions in the range of 0.1 to 20% by weight. desirable. If the content of these metal ions is less than the lower limit, the antibacterial activity is lowered. If the content of these metal ions exceeds the upper limit, the antibacterial activity is not increased any more, and insoluble metal salts precipitate on the surface of the zeolite. have.

Preferable compounding ratio of the antimicrobial composition contained in the antimicrobial resin composition of this invention is 0.1-20 weight% with respect to resin, More preferably, it is 0.1-10 weight%. If it is less than 0.1 weight%, it is difficult to exhibit sufficient antimicrobial property to a resin composition, and even if it adds more than 10 weight%, there is no big improvement of antimicrobial property, and it causes problems, such as a molding defect and discoloration.

The organic compound (PIBSA) represented by the following formula (II) is prepared by thermally reacting highly reactive polyisobutylene (HRPIB) with maleic anhydride (MA) and the content of maleic anhydride (MA). This is about 8% by weight.

[Formula II]

The organic compound of the structural formula is useful as a compatibilizer because the main chain is composed of polybutene having a nonpolar structure and a maleic anhydride structure having a terminal polarity, and is particularly useful for kneading a nonpolar polymer and an inorganic filler. It is also known that maleic anhydride at the end is acidic and has an excellent bactericidal effect.

The resin used in the present invention may be any of natural resins, semi-synthetic resins and synthetic resins, and any of thermoplastic resins and thermosetting resins may be used. Specific resins include molding plastics, fiber plastics and rubber-like plastics. For example, polyethylene, polypropylene, vinyl chloride, ABS resin, nylon, polyester, polyvinylidene chloride, polyamide, polystyrene, poly Acetyl, polycarbonate, acrylic resins, fluororesins, polyurethane elastomers, polyester elastomers, melamine resins, urea resins, tetrafluoroethylene resins, unsaturated polyester resins, and the like, but the present invention is not limited to the resins listed above.

Antimicrobial zeolite is a natural zeolite or a synthetic zeolite, characterized in that the aluminosilicate having a three-dimensional skeleton structure represented by the following formula (I), the method of substitution of inorganic metal ions according to known groups known.

The amount of the organic compound (PIBSA) according to the present invention is suitably 0.1% to 10.0% by weight, preferably 0.5% to 5.0% by weight, and less than 0.1% by weight, based on the weight of the zeolite to be surface treated. If the effect as a fungicide is insignificant and more than 10.0% by weight, the physical properties of the resin, in particular the heat resistance temperature is lowered.

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

Example 1 Preparation of Antimicrobial Resin Composition

end. Ion exchange of zeolite

1.5 kg of A-type zeolite (A) powder was added to 3.5 liters of purified water to form a slurry, and then the pH was adjusted to 5-8 by adding an aqueous nitric acid solution while stirring. Here, 58 g of silver nitrate was added to 5.5 liters of a mixed aqueous solution made of 850 g of zinc nitrate, and the slurry was stirred at a temperature of 25 to 55 ° C. for 10 to 15 hours to perform an ion exchange reaction. The prepared slurry was filtered and excess silver and zinc ions were washed sufficiently with purified water. This was dried and pulverized at a temperature of 120 ° C. to obtain an antimicrobial zeolite.

I. Surface treatment

1 kg of the prepared antimicrobial zeolite (A) was added to 3 liters of hexane to form a slurry, and then, while stirring, PIBSA was added to 0.45 Wt% based on the weight of zeolite and stirred at room temperature for 30 minutes, and then hexane was removed through vacuum distillation. do. The slurry was then filtered and dried to obtain a surface treated antimicrobial composition.

Comparative Example 1 Preparation of Antimicrobial Resin Composition

end. Ion exchange of zeolite

Antimicrobial zeolite was obtained through the same procedure as "A" of Example 1.

I. Surface treatment

1 kg of the prepared antimicrobial zeolite (A) was added to 3 liters of hexane to form a slurry, followed by adding 5.0 Wt% of the octyltrimethoxysilane to the zeolite weight while stirring and stirring at room temperature for 30 minutes, followed by Vacuum Distillation. Remove hexane through. The slurry was then filtered and dried to obtain a surface treated antimicrobial composition.

Comparative Example 2 Preparation of Antimicrobial Resin Composition

end. Ion exchange of zeolite

Antimicrobial zeolite was obtained through the same procedure as "A" of Example 1.

I. Surface treatment

After adding 1 kg of the prepared antimicrobial zeolite (A) to 3 liters of hexane to form a slurry, 3.5Wt% of phenyltrimethoxysilane was added to the zeolite weight while stirring, and stirred at room temperature for 30 minutes, followed by Vacuum Distillation. Remove hexane through. The slurry was then filtered and dried to obtain a surface treated antimicrobial composition.

Comparative Example 3 Preparation of Antimicrobial Resin Composition

end. Ion exchange of zeolite

Antimicrobial zeolite was obtained through the same procedure as "A" of Example 1.

I. Surface treatment

1 kg of the prepared antimicrobial zeolite (A) was added to 3 liters of hexane to form a slurry, and after stirring, 3-methoxypropyltrimenoxysilane was added with 2.8 Wt% of the zeolite weight and stirred at room temperature for 30 minutes. Remove hexane through vacuum distillation. The slurry was then filtered and dried to obtain a surface treated antimicrobial composition.

Example 2 Preparation of Antimicrobial Resin Composition

3.0 wt% of the antimicrobial compositions prepared in Examples 1 and Comparative Examples 1 to 3 were added to the polyethylene resin, a Henschel mixer was added and kneaded uniformly for about 10 minutes, followed by extrusion molding using a single screw extruder to prepare pellets. .

Test Example Antibacterial Test

In order to test the antimicrobial ability of the prepared antimicrobial composition was tested for antimicrobial properties as follows. Test strains were measured using Escherichia coli (Escherichia coil), the bacteria were incubated at 30 ℃ for 24 hours in agar medium and inoculated with one colony in a broth medium, followed by shaking culture at 30 ℃ for 7 hours. This bacterial solution was diluted to 2-5 × 10 ⁵ cfu / ml using sterile phosphate buffer solution, and then inoculated into the antimicrobial resin composition prepared above. Initial inoculation number was 3.2 × 10 ⁴ .

The viable cell count of E. coli measured after 24 hours has been shown in the table below.

Table 1: Measurement of Antimicrobial Test Results

Sample (antibacterial resin composition) Viable count Example 1 0.7 × 10 ⁴ Comparative Example 1 2.0 × 10 ⁴ Comparative Example 2 2.3 × 10 ⁴ Comparative Example 3 2.8 × 10 ⁴

As can be seen from the table, the antimicrobial activity of the antimicrobial resin composition prepared in Example 1 was found to be the most excellent. This means that surface treatment of the antimicrobial zeolite with PIBSA is more effective than surface treatment with the organic compounds used in the comparative examples.

Claims (3)

An antimicrobial zeolite composition prepared by surface treatment of an antimicrobial zeolite of formula (I) with Poly Isobutylene Succinic Anhydride (PIBSA), an organic compound represented by formula (II) represented by formula (II) [Formula I] xM ₂ / nO Al ₂ O ₃ ySiO ₂ zH ₂ O (In Formula I, M is zinc, copper and silver ions, the content of silver ions is in the range of 0.1 to 10% by weight, the content of copper ions is in the range of 0.1 to 15% by weight, and the content of zinc ions is 0.1 to 20% by weight, n denotes the valence of the ion, x and y denote the coefficients of the metal oxide and silica, and z denotes the number of crystallized water.) [Formula II]

delete Adding purified water to the zeolite powder to form a slurry; Adjusting the pH to 5 to 8 by adding an aqueous nitric acid solution while stirring the slurry; Injecting and stirring an aqueous solution of at least one ion-exchangeable metal selected from zinc, copper, silver, mercury, tin, lead, bismuth, cadmium, chromium and thallium ions into the slurry, followed by ion exchange reaction; The method for producing an antimicrobial zeolite composition comprising the step of surface treatment with Poly Isobutylene Succinic Anhydride (PIBSA), an organic compound represented by the following formula (II), by filtration, washing and drying the slurry subjected to the ion exchange reaction. [Formula II]