JP2002235008A - Organic-inorganic composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organic-inorganic composite material comprising a compound exhibiting excellent antibacterial and/or antifungal activity, and useful for mixing with a cement material. SOLUTION: The organic-inorganic composite material consists of organic polymer domains and inorganic domains. The organic polymer domain is a polymer having antibacterial and/or antifungal functional groups, and in the inorganic domain, one or more kinds of divalent metal atoms and silicon atom are linked with each other by forming a siloxane bond of the silicon atom, and the organic polymer domain and the inorganic domain have chemical bond.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic polymer domain-inorganic domain composite material having antibacterial and / or antifungal properties.

[0002]

2. Description of the Related Art From the viewpoints of prevention of food poisoning and hygiene management, development of materials having excellent antibacterial properties is expected. As the antibacterial material, an inorganic antibacterial agent using a metal having antibacterial properties such as silver or copper and a bactericidal organic compound having a specific chemical structure are known. For example, JP-A-9-30915 discloses a sintered body using silica gel as a base material and carrying an antibacterial metal such as silver or copper. However, in this method, a complicated operation such as sintering is required, so that the productivity is not sufficient, and the amount that can contain an antibacterial metal is about several percent.

[0003] Japanese Patent Application Laid-Open No. 10-130105 discloses a method of supporting an organic antifungal material between layers of a layered silicate. However, there are cases where the sustainability of the effect is not sufficient only by carrying an organic substance. Further, in recent years, a system using a photocatalyst has been widely studied.
000-17356 discloses a photocatalytic alloy containing copper and titanium. However, although the photocatalyst is effective in a bright window where sunlight is directly inserted, there is a problem that the brightness is insufficient around a so-called water area such as a bathroom or a kitchen, and a sufficient effect is not exhibited. .

[0004] On the other hand, a composite material obtained by combining two or more materials having different properties can obtain excellent properties that cannot be obtained by a single material. Among them, composite materials composed of a combination of organic polymer materials and inorganic materials, especially materials in which organic polymer materials and inorganic materials called nanocomposite materials are compounded at the nanometer size level, have new structures derived from their structures. Expectations for application development are gathering for various physical properties.

For example, a water-soluble polymer enters between the layers of calcium silicate hydrate, and a composite material mainly composed of an inorganic material (H. Matsuyama, et al., Chemistry of Materials, 11,
[1], 16-19 (1999)), but there is no application to antibacterial materials.

[0006]

An object of the present invention is to provide an organic-inorganic composite material having antibacterial and / or antifungal properties.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the organic polymer domain is a polymer having an antibacterial and / or antifungal functional group, and the inorganic domain is At least one divalent metal atom and a silicon atom are bonded via a siloxane bond of the silicon atom,
In addition, they have found that a composite material in which an organic polymer domain and an inorganic domain have a chemical bond has antibacterial properties and / or antifungal properties, and have led to the present invention.

That is, the present invention is as follows. (Claim 1) A composite material comprising an organic polymer domain and an inorganic domain, wherein the organic polymer domain is a polymer having an antibacterial and / or antifungal functional group, and the inorganic domain comprises one or more An organic-inorganic composite material in which a valence metal atom and a silicon atom are bonded via a siloxane bond of the silicon atom, and wherein the organic polymer domain and the inorganic domain have a chemical bond. (Claim 2) a silicate anion formed from a silicate compound or a silicon halide in the presence of an aqueous medium,
The organic-inorganic composite material according to claim 1, which is produced by contacting a polymer having an antibacterial and / or antifungal functional group with a divalent metal cation formed from a divalent metal salt. (Claim 3) The organic-inorganic composite material according to claim 1 or 2, wherein the polymer contains a quaternary ammonium salt in the molecule. (Claim 4) The organic-inorganic composite material according to claim 1, 2 or 3, wherein the divalent metal atom comprises a transition metal atom.

Hereinafter, the present invention will be described in detail. First, a silicon oxide having a siloxane bond, which is a component of the composite material having antibacterial and / or antifungal properties in the present invention,
The polymer having a divalent metal atom and an antibacterial and / or antifungal functional group will be described in detail. In the present invention, the inorganic domain needs to have a siloxane bond of a silicon atom chemically bonded to a divalent metal atom, and further has a chemical reaction with a polymer having an antibacterial and / or antifungal functional group described below. The composite material is formed by the effective bonding. That is, due to the presence of these chemical bonds, antibacterial performance and antifungal performance are maintained for a long period of time. In addition, by combining an inorganic domain having antibacterial and / or antifungal properties with an organic polymer domain having antibacterial and / or antifungal properties,
It is possible to select an effective antibacterial property and / or antifungal property against a wide variety of bacterial species, or a strong antibacterial and / or antifungal property against a specific bacterial species.

In the present invention, the ratio of the divalent metal atom (M), which is a component of the inorganic domain, to the silicon atom (S) having a siloxane bond is not particularly limited, but is preferably M / S (number of atoms). Ratio) is 0.05 to 5.0, more preferably 0.1 to 5.0, and still more preferably 0.3 to 5.0.
3.0, most preferably 0.3 to 2.0. In the present invention, divalent metal atoms are beryllium, magnesium, calcium, strontium, alkaline earth metal atoms of barium, copper, zinc, nickel, iron, manganese, chromium, cobalt, etc. Any existing metal atom may be used, and a single metal atom or a combination of two or more metal atoms may be used.

Among them, transition metal atoms such as copper, zinc, manganese, and cobalt are preferably used because they have high antibacterial properties. Such divalent metal atoms can be
By using a compound such as a sulfate, an acetate, a chloride, a hydroxide, an oxide, or a carbonate as a raw material, the compound can be introduced into the composite material. Among these compounds, when the solubility in an aqueous medium described later is 1% by mass or more, it is preferable because divalent metal atoms can be introduced into the composite material in an ionic state. More preferred solubility is 5% by mass or more.

On the other hand, silicon atoms are present as a form having siloxane bonds in the composite material, and the source thereof is not particularly limited as long as it can form silicate anions in an aqueous medium. Examples of the silicon atom supply source include silicates such as sodium orthosilicate and sodium metasilicate, inorganic silicate compounds such as silicic acid and silica, tetraethoxysilane, tetramethoxysilane, and various silane coupling agents. Examples thereof include silicate compounds such as organic silicon compounds such as alkoxides and silicon halides typified by silicon tetrachloride. Among these, sodium orthosilicate, alkali metal silicates such as sodium metasilicate, silicic acid, silicate compounds such as colloidal silica and silicon halide are easy to handle, and
It is preferably used because it can be obtained at low cost. In particular, alkali metal silicates, silicic acids and silicon halides are suitable for use in combination with divalent metals having antibacterial properties since many divalent metals can be introduced into the composite material. The alkali metal silicate is a Japanese industrial standard (JIS K14) which is used industrially.
No. 08, No. 08-66).

The composition ratio (M / S) of such metal atoms can be determined by, for example, converting a measurement value obtained by X-ray fluorescence spectrometry according to a separately prepared calibration curve. In the present invention, a silicon atom in a composite material exists as an oxide having a siloxane bond, and the silicon atom is bonded to a divalent metal atom via an oxygen atom. The bond can be confirmed by infrared spectroscopy that the absorption of the siloxane bond is observed on the low wavenumber side. That is, when a silicon atom is bonded to a siloxane bond typified by silica gel, the absorption of the siloxane bond is observed at around 1090 cm ^-1 by infrared spectroscopy. When it is combined with, it is observed on the lower wavenumber side. For example, when the divalent metal atom (M) is calcium, the absorption wave number of siloxane shifts to 970 cm ^-1 . Naturally, the low wave number absorption of the infrared absorption representing the siloxane bond varies depending on the type and amount of the divalent metal atom bonded, but in any case, it is 1090 cm.
It is characterized by being observed on the lower wavenumber side from around ^-1 .

In the present invention, examples of the polymer having an antibacterial and / or antifungal functional group include a polymer having a 6-membered heterocyclic structure directly bonded to a main chain or a side chain, and one or more nitrogen atoms in the ring. , A polymer having a haloalkylthio functional group in the main chain or side chain, a polymer having an azole derivative functional group in the main chain or side chain, or a quaternary ammonium base in the main chain or side chain And a polymer in which a compound known as a known antibacterial agent or antifungal agent is bound by chemical means. These polymers are appropriately selected depending on the use of the antibacterial and / or antifungal agent so as to exhibit suitable antibacterial and antifungal performance. In addition, these polymers can be appropriately mixed or copolymerized within a range having a chemical bond with an inorganic domain according to the purpose.

Although the molecular weight of the polymer having such a functional group is not particularly limited, a polymer containing an antibacterial and / or antifungal functional group is preferably used from the viewpoint of antimicrobial and / or antifungal durability. The degree of polymerization of the constituent monomers is 1
A polymer having a polymerization degree of 0 or more, more preferably 100 or more is used. The upper limit is appropriately selected from the viewpoint of ease of handling such as viscosity according to the method of using the antibacterial agent. In the present invention, the polymer having an antibacterial and / or antifungal functional group is a quaternized dimethylaminoethyl (meth) acrylate having such a functional group, diallyldimethylammonium chloride, 4-vinylbenzyltrimethylammonium Chloride, 4-vinyl-
It may be a homopolymer obtained by polymerizing a monomer such as 1-methylpyridinium bromide, or a copolymer with a monomer as exemplified below.

The monomers used for such copolymerization include, for example, vinyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate. ) Acrylate,
(Meth) acrylic acid and its alkali metal salt, itaconic acid and its alkali metal salt, 2- (meth) acryloyloxyethylsuccinic acid and its alkali metal salt, 2-
(Meth) acryloyloxyethyl phthalic acid and its alkali metal salt, 2- (meth) acryloyloxyethyl hexahydrophthalic acid and its alkali metal salt, 2-
(Meth) acrylamide-2-methylpropanesulfonic acid and its salt, styrenesulfonic acid and its salt, vinylsulfonic acid and its salt, 2-sulfoethyl (meth) acrylate and its salt, 2- (meth) acryloyloxyethylphosphoric acid and Its salts, (meth) acrylamide, (meth) acryloylmorpholine, vinylpyridine, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, N N, N'-dimethylaminoethyl (meth) acrylate, N, N'-diethylaminoethyl (meth) acrylate, N, N'-dimethylaminoneopentyl (meth) acrylate, N-vinyl-
2-pyrrolidone, diacetone acrylamide, N-methylol (meth) acrylamide, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate (number average molecular weight of polyethylene glycol 400) , Methoxypolyethylene glycol (meth) acrylate (number average molecular weight of polyethylene glycol 1000), butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (Meth) acrylate, nonylphenoxyethyl (meth) acrylate, isoborny (Meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrafurfuryl (meth) acrylate, benzyl (meth) acrylate, methyl (Meth) acrylate,
Ethyl (meth) acrylate, styrene and the like.

Examples of the polymer having a functional group having antibacterial and / or antifungal properties include compounds such as methyl glycol chitosan iodide in which the nitrogen atom in the ring of the polysaccharide is quaternized. Natural polymers and synthetic polymers such as polyamide, polyurethane, polyurea, and polyester chemically introduced by a method such as grafting a functional group having antibacterial and / or antifungal properties can also be used. Among them, the polymer having a quaternary ammonium base is preferably used from the viewpoint of easy production and availability at low cost.

In the present invention, when a polymer having an antibacterial and / or antifungal functional group is dissolved in an aqueous medium described below, it is preferable because a composite material can be easily produced. In the present invention, the aqueous medium is a solvent containing 10% by mass or more of water at room temperature, and preferably a solvent containing 50% by mass or more of water. Solutes that can be mixed with water in an aqueous medium include various water-soluble solvents such as alcohols, ketones, esters, dimethylformamide and dimethylsulfoxide, and inorganic solvents such as hydrochloric acid, sulfuric acid, acetic acid, and paratoluenesulfonic acid. , Organic acids, inorganic salts such as sodium chloride and sodium acetate, various alkalis such as alkali metal hydroxides, ammonia and amines, various surfactants such as nonionic, anionic, cationic and silicone type And the like.

The fact that the organic polymer domain and the inorganic domain contain a chemical bond is characterized by the fact that they are thoroughly washed, dried, and analyzed by infrared spectroscopy. And absorption specific to an inorganic domain represented by a siloxane bond are observed. The form of the chemical bond is not particularly limited, and examples thereof include a hydrogen bond, an ionic bond, and a covalent bond. Among these, ionic bonds and covalent bonds have a strong bond strength and are preferred bonding forms. From the viewpoint of simplicity of production, ionic bonding is more preferable. The chemical bond is formed, for example, between a functional group having antibacterial and / or antifungal properties of the organic domain or a functional group used in copolymerization and the inorganic domain.

[0020] The composite material of the present invention can be prepared in the presence of an aqueous medium.
It is produced by contacting a silicate anion formed from a silicate compound or a silicon halide, a polymer having an antibacterial and / or antifungal functional group, and a divalent metal cation formed from a divalent metal salt. . The mixing conditions in this case are not particularly limited, but when it is necessary to finely disperse the composite material, a dispersing / emulsifying apparatus having high-speed rotating blades called a disperser or a homogenizer is also preferably used.

The order of addition of each component is not particularly limited. However, depending on the pH at the time of production, a precipitate may be formed at the time of mixing two of the three components. In addition, it is necessary to appropriately examine production conditions such as pH adjustment and the order of addition. When the silicate compound is an organic silicon compound represented by an alkoxide, it is generally used after hydrolyzing the silicon compound. As a method of hydrolyzing the organic silicon compound, a known method can be used.

The formation reaction of the composite material of the present invention is characterized in that it usually proceeds promptly by mixing at room temperature. When an organic silicon compound is used as a source of silicon atoms, it is necessary to carry out hydrolysis in advance. Is preferably used after the reaction is advanced, or a method in which an organic silicon compound is hydrolyzed and used in an acidic region. The solvent used when the organic silicon compound is hydrolyzed in advance needs to contain water, and a solvent containing water at 10% by mass or more at room temperature is preferably used. As the solvent, not only water but also a water-soluble solvent such as acetone, methanol, ethanol, dimethyl sulfoxide, or a mixed solvent of a mixture thereof and water may be used. At this time, the polymer does not necessarily need to be completely dissolved, but it is preferable that the polymer is completely dissolved in order to cause a uniform reaction.

The composite material of the present invention may contain not only the above-mentioned divalent metal atoms but also, for example, monovalent metal atoms such as sodium, potassium and silver. Among them, a metal atom having antibacterial property alone, such as silver, is preferably used because the antibacterial property of the composite material is improved. On the other hand, the composite material of the present invention may contain a trivalent metal atom such as aluminum and iron. In particular, among these, the aluminum atom is preferably replaced with the silicon atom in the inorganic domain constituting the composite material, and the bond with the organic polymer domain may be strong in some cases. The substitution ratio of aluminum atoms to silicon atoms having a siloxane bond is not particularly limited.
It is preferred that 15 atom% is replaced by aluminum atoms.

The presence of the aluminum atom replacing the silicon atom can be confirmed by the signal shift of silicon in ²⁹ Si nuclear magnetic resonance spectroscopy (NMR method). Examples of the source of aluminum atoms include inorganic aluminum compounds such as aluminum chloride and sodium aluminate, and alkoxides represented by triethoxyaluminum. next,
The method of using the antibacterial and / or antifungal composite material of the present invention will be described.

The method of using the antibacterial and / or antifungal composite material of the present invention is not particularly limited. For example, a method of mixing with a cement material and using it as a cement-based hardened material such as joint material, a method of mixing and using a caulking material, a method of mixing and using a resin, a method of mixing with a coating material represented by latex And a method of using it as a coating film. In particular, the method of mixing and using the cement-based material is such that the organic polymer domain constituting the composite material of the present invention forms a chemical bond, and furthermore, it is expected that the inorganic domain also has an interaction, It is preferably used because it can be mixed without substantially lowering the strength of the cement-based cured product.

In the present invention, the fact that no substantial decrease in the strength of the cement-based cured product is accompanied means that the decrease in strength when the composite material of the present invention is mixed is limited to a range due to a change in specific gravity. However, this includes a case where there is no change in strength and a case where strength is improved. Since the composite material of the present invention becomes a composite material having transparency by adjusting the production conditions, the composite material is suitably used for applications requiring transparency. Since the antibacterial and / or antifungal composite material of the present invention has hydrophilicity, when it is used for a coating, not only antibacterial and antifungal properties but also antiadhesive properties due to hydrophilicity and easy cleaning properties can be obtained.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically by way of examples, but the present invention is not limited to these examples. In the present invention, the antibacterial activity test was performed by the following method. First, a dispersion having a predetermined concentration of a specimen is prepared on a mass / volume basis using sterilized purified water, and then, after sterilization and dissolution, Mueller Hint maintained at 50 to 60 ° C.
A predetermined amount of the prepared dispersion was added to on Agar (Difco), mixed well, and then dispensed and solidified in a petri dish to prepare a test plate containing a test substance of a predetermined concentration. Also,
Separately, subcultured test bacteria (Escherichia coli: Escheric
ia coli IFO 3972)
was inoculated into r Hinton Broth (Difco), 35 ± 1 ℃, after 18 to 20 hours of culture, the number of bacteria 10 ⁶
The bacterial solution obtained by diluting with the same medium so as to be / ml was used as the bacterial solution for inoculation. The test inoculation bacterial solution is streaked about 1-2 cm on the test plate using a resin loop (inner diameter: about 1 mm), and cultured at 35 ± 1 ° C. for 18-20 hours. The presence or absence of growth was determined.

[0028]

Example 1 Polydiallyldimethylammonium chloride (Aldrich Reagent Mw 100,000-200,000)
9 parts by mass of a 0% by mass aqueous solution, 14 parts by mass of purified water, 20 parts by mass of sodium metasilicate / 9-hydrate, 0.8 parts of caustic soda
The parts by mass were mixed and stirred for 30 minutes to prepare a mixed solution. Next, 66.5 parts by mass of a 20% by mass aqueous solution of calcium nitrate tetrahydrate was mixed to obtain a dispersion. Next, the obtained dispersion was diluted 5-fold, centrifuged using an MP4 centrifuge manufactured by International Equipment Company, and a washing operation of adding purified water and washing was repeated 5 times. After drying under reduced pressure at 60 ° C. and about 1 kPa for 8 hours or more and measuring by infrared spectroscopy,
2930 cm ^-1 vicinity to the absorption of organic components, is observed components derived from siloxane bonds near 970 cm ^-1, it was confirmed that the composite material of the present invention are present. The composite material obtained by washing and drying was used as a specimen, and 4.0 mass / vol%, 2.0 mass / vol%, 1.0 mass / vol%, and 0.6 mass of the agar medium. / Vol%, the antibacterial properties were evaluated. In the case of 1.0% by mass / volume or more, growth of Escherichia coli was not observed, and it was confirmed that the composition had antibacterial properties.

[0029]

Example 2 Polydiallyldimethylammonium chloride (Aldrich Reagent Mw 100,000-200,000)
To 24 parts by mass of a 0% by mass aqueous solution, 105 parts by mass of purified water, 20 parts by mass of sodium metasilicate / 9-hydrate, 0.1 part of caustic soda.
Two parts by mass were mixed and stirred for 30 minutes to prepare a mixed solution. Next, a 20% by mass aqueous solution of zinc sulfate heptahydrate 4
0.5 parts by mass were mixed to obtain a dispersion. Next, when the presence of the composite material was confirmed in the same manner as in Example 1, it was confirmed that the composite material was present. The composite material obtained by washing and drying was used as a specimen, and the volume of the agar medium was 4.
When antibacterial properties were evaluated by mixing 0% by mass / volume, 2.0% by mass / volume, 1.0% by mass / volume, and 0.6% by mass / volume, even when 0.6% by mass / volume was mixed. No growth of Escherichia coli was observed, indicating that it had antibacterial properties.

[0030]

Comparative Example 1 An inorganic particle dispersion was prepared in the same manner as in Example 1 except that polydiallyldimethylammonium chloride (Reagent Mw 100,000 to 200,000, manufactured by Aldrich) was not added. After washing and drying, a white powder was obtained. The white powder obtained by washing and drying was used as a sample, and was 4.0 mass / volume% based on the volume of the agar medium.
When the antibacterial activity was evaluated by mixing 2.0% by mass / volume, 1.0% by mass / volume, and 0.6% by mass / volume, the growth of Escherichia coli was recognized even when the mixture was 4.0% by mass / volume. Was done.

[0031]

Industrial Applicability The composite material of the present invention exhibits excellent antibacterial and / or antifungal properties, and is particularly preferably used in combination with a cement-based material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 3/03 CEZ C08J 3/03 CER 3/075 CEZ CEZ C08K 3/34 // C04B 16/00 F term (Reference) 4F070 AA12 AA75 AC22 AC52 BA07 CB03 CB11 4H011 AA02 AA03 BA01 BB04 BB19 BC18 BC19 DA01 DD01 DD07 DE14 DH02 DH07 DH25 4J002 AB001 BG071 CF001 CK021 CL001 CP032 DJ006 DJ016 EX036 HA04

Claims (4)

[Claims] 1. A composite material comprising an organic polymer domain and an inorganic domain, wherein the organic polymer domain is a polymer having an antibacterial and / or antifungal functional group, and the inorganic domain comprises one or more An organic-inorganic composite material in which a valence metal atom and a silicon atom are bonded via a siloxane bond of the silicon atom, and wherein the organic polymer domain and the inorganic domain have a chemical bond. 2. The composite material is formed from a silicate anion formed from a silicate compound or a silicon halide, a polymer having an antibacterial and / or antifungal functional group, and a divalent metal salt in the presence of an aqueous medium. The organic compound according to claim 1, which is produced by contacting the organic compound with a divalent metal cation.
Inorganic composite materials. 3. The organic-inorganic composite material according to claim 1, wherein the polymer contains a quaternary ammonium salt in the molecule. 4. The organic-inorganic composite material according to claim 1, wherein the divalent metal atom comprises a transition metal atom.