KR20130128243A - Organic/inorganic hybrid precursor for supporting hydrophobic antibacterial material and method for preparing the antibacterial film by using thereof - Google Patents

Abstract

The present invention relates to an organic/inorganic hybrid material and a method for preparing the same, wherein the material has a structure of chemical formula 1. In the chemical formula, A includes a hydrophobic segment and at least three hydroxyl groups and forms urethane bonding, B contains at least two isocyanate groups and forms urethane bonding, C contains a hydroxyl group and an alkoxysilane group, or an amine group and alkoxysilane group and forms urethane bonding and urea bonding, and D contains a hydrophilic segment and two or more hydroxy groups and forms urethane bonding. [Reference numerals] (AA) Germs) Staphylococcus aureus (Gram+) ATCC25923;(BB) Germs) Bacillus cereus (Gram+) ATCC11778;(CC) Germs) Esherichia coli (Gram-) ATCC6750;(DD) Germs) Candida albicans ATCC10231

Description

Organic / inorganic hybrid precursor for supporting hydrophobic antibacterial material and method for preparing the antibacterial film by using}

The present invention relates to a reactive precursor of an organic / inorganic hybrid type having both a hydrophilic segment and a hydrophobic segment and having an alkoxysilane group and a reactive precursor having an alkoxysilane group, And an antibacterial film.

Recently, it has become a social phenomenon to pursue cleanliness and safety beyond the convenience and usefulness of products due to the improvement of living standards and living environment. Antibacterial products using antibacterial agents, antibacterial household appliances and products capable of maintaining fresh lead Demand is soaring and as the type and quantity of materials imported from abroad increases, it must be able to prevent contamination and corruption that may be caused by microorganisms during packaging and distribution of materials.

Antimicrobial packaging has various antimicrobial properties imparted to the packaging material, thereby increasing the shelf life of the material. Among them, the method of imparting the antimicrobial property to the material itself is advantageous in that it can control the transfer rate of the antimicrobial substance as well as the secondary contamination as compared with the case of adding preservative or antimicrobial substance directly to the material. Methods for adding an antimicrobial substance to a film of a packaging material include a coating method in which an antimicrobial substance is first added to a polymer solution and then a coating is formed by directly applying or spraying the antimicrobial substance onto the object and a casting method casting method, and a method of producing a film by mixing a plastic polymer powder and an antimicrobial material and heating or pressing or extruding the same. The most efficient process is a coating method which is simple in production process and low in production cost. There are sputtering, chemical vapor deposition (CVD), ion implantation, and vacuum deposition methods. However, these methods have disadvantages such as experimental equipment and costly disadvantages. As an alternative to this, there is a coating method using a sol-gel process, which can provide high uniformity and high purity and can be synthesized at a low temperature, thus saving energy, reducing evaporation loss, reducing air pollution, Is possible.

The antimicrobial material used in the production of the film should have a chemically stable structure, and should be properly introduced into the food even during distribution for a long time, and safety should be ensured even if it is synthesized. It should also have a broad spectrum of activity across different microorganisms and a low toxicity profile for higher organisms. So far, many antimicrobial materials such as chlorine, organic, inorganic (Ag, Zn, Cu) have been developed and applied. However, due to problems of cytotoxicity, stability and dissolution, Researches are being actively conducted on natural extracts or natural antimicrobial substances which are harmless to the human body and are more environmentally friendly. However, until now, there have been no studies to produce antibacterial films using natural materials as antimicrobial agents, and there are few reports and patent reports on the production and development of antibacterial films using amphiphilic polymers.

Therefore, in the present invention, an organic / inorganic hybrid antimicrobial material containing a hydrophobic natural antimicrobial substance at a high concentration is easily and conveniently prepared by using an amphipathic polymer in the form of an organic / inorganic hybrid, through a sol-gel reaction, A method for producing an antibacterial film by curing by a one-shot process at room temperature (a supported organic / inorganic hybrid material) was developed.

In the present invention, an organic / inorganic hybrid type reactive precursor in which an amphiphilic polymer and an alkoxysilane group are present at the same time is synthesized, and a hydrophobic natural antimicrobial substance is supported by a one-shot process through a sol- The objective of the present invention is to produce an antibacterial film in the form of an organic / inorganic hybrid.

In order to achieve the above object, the present invention provides an organic / inorganic hybrid type reactive precursor in which an amphiphilic polymer having a structure represented by the following general formula (1) and an alkoxysilane group are simultaneously present.

(In the formula 1,

A is a substance comprising a hydrophobic segment and three or more hydroxyl groups, and reacts with the isocyanate group of B to form a urethane bond;

Wherein B is a substance containing at least two isocyanate groups, one isocyanate group reacts with the hydroxyl group of A to form a urethane bond, and the other reacts with the hydroxyl group or amine group of the C to form a urethane bond or a urea bond Or reacts with the hydroxyl group of D to form a urethane bond;

Wherein C is an acrylate or methacrylate having a hydroxyl group, the hydroxy group reacts with the isocyanate group of B to form a urethane bond;

Wherein D is a substance comprising a hydrophilic segment and two or more hydroxy groups, and reacts with the isocyanate group of B to form a urethane bond)

The present invention also provides an organic / inorganic hybrid nanoparticle capable of supporting various hydrophobic antimicrobial substances through a sol-gel reaction using the reactive precursor.

In the present invention, an organic / inorganic hybrid type reactive precursor in which an amphipathic polymer and an alkoxysilane group are present at the same time is synthesized, and a hydrophobic natural antimicrobial substance is supported on a one-shot process through a sol- / Inorganic hybrid type material to provide a transparent and uniform antibacterial film carrying a hydrophobic natural antimicrobial substance.

1 is a diagram of a reactive precursor in an organic / inorganic hybrid form in which an amphiphilic polymer and an alkoxysilane group are simultaneously present according to the present invention.
Fig. 2 is a photograph showing reactive precursor particles of an organic / inorganic hybrid type synthesized according to the present invention.
FIG. 3 is a graph showing the results of solubilized silica prepared by dissolving an amphipathic reactive precursor synthesized according to the present invention in an organic / inorganic hybrid form and tetraethyl orthosilicate (TEOS) Type hybrid material.
FIG. 4 is a photograph showing an organic / inorganic hybrid material on which a hydrophobic natural antimicrobial substance manufactured by a one-shot process is supported according to the present invention and an antibacterial film prepared by curing the same.
FIG. 5 is a photograph showing antimicrobial activity of an organic / inorganic hybrid material on which a hydrophobic natural antimicrobial substance prepared according to the present invention is supported.

The present invention relates to a process for synthesizing a polymer having a hydrophobic segment and a hydrophilic segment at the same time and having an alkoxysilane group bonded thereto and using the polymer as a precursor to form a hydrophilic segment having hydrophilic natural antibacterial substance- It is characterized by the production of materials in the form of hybrids.

The alkoxysilane group-bonded polymer precursor according to the present invention is an organoalkoxysilane formed by chemically bonding four kinds of materials A, B, C and D as shown in the following Chemical Formula 1.

[Formula 1]

FIG. 1 is a diagram showing a bonding structure between the materials of Formula 1. FIG.

Referring to FIG. 1,

A is a substance having a hydrophobic segment and three or more hydroxyl groups, and each of the hydroxyl groups reacts with an isocyanate group to form a urethane bond. Any material having the above characteristics may be applied to the present invention, but preferably includes polypropylene triol or glycerol.

In the present invention, the polypropylene triol includes an oligomer and a polymer in which a propylene ether group is bonded and extended to glycerol. By controlling the molecular weight of the polypropylene triol, the size of the composite nanoparticles produced can be varied.

The role of B is mediated by A and C, A and D, and is a substance having two or more isocyanate groups. One isocyanate group forms a urethane bond with the hydroxyl group of the A and the other isocyanate group forms a urethane bond with the hydroxyl group of the C or D or reacts with the amine group of the C to form a urea bond. As the B, triisocyanate is also applicable, but diisocyanate can be preferably used. The diisocyanate may be any material used for urethane synthesis such as toluene diisocyanate (TDI), isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, tolylidine diisocyanate have.

C is a functional group which binds to B and has a hydroxyl group or an amine group and is a substance having an organic alkoxysilane group simultaneously to form an organic silica nanoparticle according to a sol-gel reaction.

The D is characterized by having a hydrophilic segment for water dispersibility and has urethane bond with the isocyanate group of the B having two or more hydroxy groups. Preferred materials include polyethylene glycol.

Representative materials of A, B, C, and D applicable to the present invention are shown in Table 1 below.

matter constitutional formula Chemical name


A

Glycerol

m = 1 to 50, n = 0 to 50, p = 0 to 50 Polypropylene triol















B

,

2,4-toluene Diisocyanate ,

2,6-toluene Diisocyanate

Isophorone Diisocyanate

Methylene Diisocyanate

4,4'-methylene Diphenyl Diisocyanate

Hexamethylene Diisocyanate

xylene Diisocyanate

Tolidine Diisocyanate



C

Methoxy ( Polyethyleneoxy ) Propyl trimethoxysilane

Hydroxymethyltriethoxysilane

Aminopropyltriethoxysilane




C

Bis (trimethoxy) silylpropylamine

(3- Glycidoxypropyl ) Trimethoxysilane

[2- (3,4- Epoxycyclohexyl )ethyl] Trimethoxysilane
D

Polyethylene glycol

The synthesis of reactive precursors in the organic / inorganic hybrid form in which the amphiphilic polymer having the structure of Formula 1 and the alkoxysilane group are present at the same time is carried out through the following process.

Synthesis of Amphiphilic Polymer Precursor with Alkoxysilane Groups

Step 1:

Under a nitrogen atmosphere, a material A having a hydrophobic segment, three or more hydroxyl groups and a substance B having two or more isocyanate groups was reacted at a molar ratio of 1: 3 for 4 hours at 70 to form a urethane bond between A and B .

Step 2:

A substance C having both an amine group and an alkoxysilane group or a hydroxyl group and an alkoxysilane group is added to the compound obtained in the first step and reacted to form a urethane or urea bond between B and C. The reaction molar ratio of the material C synthesized in the first step is set at 1 molar ratio.

Step 3:

(D) having a hydrophilic segment and a hydroxy group, preferably polyethylene oxide having a molecular weight of 600 to 15,000, is added to the resultant mixture obtained in the second step at a molar ratio of 1: 1 to form a urethane bond between B and D, The precursor is synthesized.

The present inventor named the amphiphilic polymer precursor having an alkoxysilane group bonded thereto synthesized in the present invention as an abbreviation of Amphiphilic Polymeric Alkoxy Silane and named APAS.

The antimicrobial film according to the present invention is produced by sol-gel reaction of an amphipathic polymer precursor (APAS) in which an alkoxysilane group exists and tetraethyl orthosilicate (TEOS) as a tetrafunctional silane compound in an organic solvent or a water mixed solvent . Tetraethylorthosilicate provides a more complex structure through a sol-gel reaction with the amphiphilic polymer precursor (APAS), thereby preventing the supported hydrophobic antimicrobial component from escaping out of the film while providing the physical properties required for film formation.

Example  One: When the alkoxysilane group is  Present Amphibian  Polymer precursor ( APAS ) Synthesis of

Under a nitrogen atmosphere, a reaction was carried out with a polypropylene triol having a molecular weight of 260 and 2,4-toluene diisocyanate at a molar ratio of 1: 3 at about 45 to 50 ° C for 4 hours.

Hydroxyethyl methacrylate was added to the resultant mixture at a molar ratio of 1: 2, followed by stirring.

An amphipathic polymer precursor (APAS) having an alkoxysilane group was synthesized by adding polyethylene oxide having a molecular weight of 1,500 at a molar ratio of 1: 5 and stirring the resultant.

2 is a photograph of an amphiphilic polymer precursor (APAS) particle synthesized according to this embodiment.

Example  2 to 4: Amphibian  Polymer precursor ( APAS ) And Tetraethyl  Orthosilicate ( TEOS)  Soluble silica ( Soluble silica ) Manufacturing of materials

As shown in the following Table 2, 5 parts by weight of the alkoxysilane-bonded amphiphilic polymer precursor (APAS) synthesized in Example 1 was mixed with 40 parts by weight of ethanol / 10 parts by weight of water (adjusted to 0.01 M of HCl as a catalyst) , And then 5, 15, and 30 parts by weight of tetraethyl orthosilicate (TEOS), which is a tetrafunctional silane compound, were mixed with each other to proceed sol-gel reaction.

As shown in FIG. 3, an organic / inorganic hybrid solution in the form of silica having a slight viscosity was prepared.

APAS TEOS Solvent Example 2 5 parts by weight 5 parts by weight Ethanol: 40 parts by weight
Water (HCl 0.01 M): 10 parts by weight Example 3 5 parts by weight 15 parts by weight THF: 40 parts by weight
Water (HCl 0.01 M): 10 parts by weight Example 4 5 parts by weight 30 parts by weight Acetone: 40 parts by weight
Water (HCl 0.01 M): 10 parts by weight

Example  5 to 7: hydrophobic antimicrobial substance Supported  Yu / Weapons hybrid  Manufacture of materials in the form of

As shown in the following Table 3, 40 parts by weight of ethanol / 10 parts by weight of water (adjusted to 0.01 M of HCl as a catalyst) was added to 5 parts by weight of an amphipathic polymer precursor (APAS) having an alkoxysilane group synthesized in Example 1 After dissolving in a mixed solvent at a predetermined concentration, Carvacrol, a hydrophobic natural antibacterial substance, and tetraethyl orthosilicate (TEOS), which is a tetrafunctional silane compound, were added and mixed to prepare a hydrophobic antimicrobial substance A solution in the form of an organic / inorganic hybrid in the form of silica was prepared.

The carbacol loading solution prepared in Example 7 was thinly coated on a slide glass and then cured at 30 캜 for about 1 hour to prepare a highly uniform and transparent antimicrobial film.

4 is a photograph of an antimicrobial film carrying a natural antibacterial substance (Carvacrol) produced according to the present invention.

APAS TEOS Carvacrol Solvent Example 5 5 parts by weight 5 parts by weight 1.853 parts by weight Ethanol: 40 parts by weight
Water (HCl 0.01 M): 10 parts by weight Example 6 5 parts by weight 15 parts by weight 2.490 parts by weight THF: 40 parts by weight
Water (HCl 0.01 M): 10 parts by weight Example 7 5 parts by weight 30 parts by weight 2.850 parts by weight Acetone: 40 parts by weight
Water (HCl 0.01 M): 10 parts by weight

Experimental Example : Antimicrobial activity test

The antimicrobial activity of the carbachol supported material prepared in Example 7 was measured according to the Paper Diffusion Method. In a sterile petri dish, 1 x 10 < ⁵ > cfu / ml of Staphylococcus strain aureus , Bacillus cereus , Esherichia coli and Candida albicans were prepared. After 40 μl of the organic / inorganic hybrid material prepared in Example 7 was absorbed and cured on a paper disc (8 mm), the bacteria were streaked and placed on a paper disc. In the case of bacteria, 24 And for 48 hours for fungi. After the incubation, it was judged that there was an antimicrobial activity when a clear zone was formed around the paper disk.

FIG. 5 is a photograph showing the antibacterial activity of a substance in the form of an organic / inorganic hybrid on which a hydrophobic antimicrobial substance prepared according to the present invention is supported, according to a strain. As shown in Figure 5, Bacillus cereus (Gram +) showed the best antimicrobial activity.

Claims (8)

Reactive precursor of organic / inorganic hybrid form represented by the structure of Formula 1, wherein the amphiphilic polymer and the alkoxysilane group are present at the same time.
[Formula 1]

(In Formula 1,
A is a material containing a hydrophobic segment and at least three hydroxyl groups, and reacted with the isocyanate group of B to form a urethane bond;
Wherein B is a substance containing at least two isocyanate groups, one isocyanate group reacts with the hydroxyl group of A to form a urethane bond, and the other reacts with the hydroxyl group or amine group of the C to form a urethane bond or a urea bond Or reacts with the hydroxyl group of D to form a urethane bond;
Wherein C is a material comprising a hydroxyl group and an alkoxysilane group, or an amine group and an alkoxysilane group, wherein a hydroxyl group or an amine group reacts with the isocyanate group of B to form a urethane bond or a urea bond;
D is a material including a hydrophilic segment and two or more hydroxyl groups, and reacts with the isocyanate group of B to form a urethane bond.)
The method of claim 1,
A is polypropylene triol or glycerol,
Wherein B is one or two or more selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, tolidine diisocyanate and ,
C is methoxy (polyethyleneoxy) propyltrimethoxysilane, hydroxymethyltriethoxysilane, aminopropyltriethoxysilane, bis (trimethoxysilylpropyl) amine, (3-glycidoxypropyl) trimeth Methoxysilane, one or two or more selected from the group consisting of [2- (3,4-epoxycyclohexyl) ethyl] trimethoxysilane,
D is polyethylene glycol,
Reactive precursor of organic / inorganic hybrid form in which amphiphilic polymer and alkoxysilane group are present at the same time.
(1) Under nitrogen atmosphere, polypropylene triol or glycerol is a di-compound consisting of toluene diisocyanate, isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, tolidine diisocyanate A first step of stirring at least one isocyanate group with at least one molar ratio of 1: 3;
(2) The process according to any one of (1) to (3) above, wherein the substance obtained in the first step is selected from the group consisting of methoxy (polyethyleneoxy) propyltrimethoxysilane, hydroxymethyltriethoxysilane, aminopropyltriethoxysilane, bis (trimethoxysilylpropyl) One or more selected from the group consisting of trimethylsilane, trimethoxysilane, trimethoxysilane and [2- (3,4-epoxycyclohexyl) ethyl] trimethoxysilane is further added at a 1: 1 reaction molar ratio, Second step;
(3) a third step of adding a polyethylene oxide having a molecular weight of 600 to 15,000 to the material obtained in the second step in a 1: 1 reaction molar ratio to stir reaction;
A method of preparing a reactive precursor in an organic / inorganic hybrid form in which an amphiphilic polymer and an alkoxysilane group are present at the same time.
An organic / inorganic hybrid reactive precursor (APAS) and tetraethyl orthosilicate (TEOS) in which an amphiphilic polymer and an alkoxysilane group are present at the same time are subjected to a sol-gel reaction under a solvent. A method for producing an organic / inorganic hybrid material.
A sol-gel reaction of an organic / inorganic hybrid reactive precursor (APAS), tetraethyl orthosilicate (TEOS), and a hydrophobic antimicrobial agent in which an amphiphilic polymer and an alkoxysilane group are present at the same time according to claim 1 Method for producing an organic / inorganic hybrid material, characterized in that the hydrophobic antimicrobial material is carried.
The method of claim 5, wherein the hydrophobic antimicrobial material is carvacrol (Carvacrol), characterized in that the hydrophobic antimicrobial material-supported organic / inorganic hybrid material manufacturing method.
The method of claim 6, wherein the antimicrobial material has antibacterial activity against Bacillus cereus. 6.
A method for producing an antimicrobial film, comprising applying and curing an organic / inorganic hybrid material loaded with a hydrophobic antimicrobial material prepared according to claim 5.

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