Antimicrobial phosphate glass

The present invention relates to antimicrobial glass based on phosphoric acid glass having antimicrobial activity, glass ceramics and ceramics obtained from the same, and glass powder and glass ceramic powder. The concept of glass powder also includes glass fibers, glass granules, and glass beads herein.

Patent Document 1 states that a very small amount of SiO₂And a very large amount of B₂O₃Or a large amount of P₂O₅Water-soluble glass used in cosmetics containing. The silver concentration of these glasses is less than 0.5% by weight. These glasses have extremely low hydrolysis resistance and have the drawback of being completely dissolved in water. The antibacterial activity of these glasses is triggered by liberated Ag and / or Cu ions.

Patent Document 2 describes silver-containing phosphate glass used as an antimicrobial substance for the treatment of wound infection in combination from Cu, Ag and Zn. The drawback of these glasses is their low hydrolysis resistance, which is shown to be completely soluble in water. These glasses are Al required for adjusting hydrolysis resistance.₂O₃Does not contain. Na with an additional 34 mol%₂The concentration of O is very high. This means that the glass is very reactive and dissolves completely relatively quickly.

The phosphoric acid glass or borosilicate glass is also well known from the following Patent Documents 3, 4, 4, 5, and 6.

In this system, its too high reactivity, which is associated with too low chemical resistance, is a disadvantage.

Patent Document 3 describes Ag in a later process stage.₂The glass fibers that are made antimicrobial by using O are described. The glass composition well known from Patent Document 3 is a small amount of Na.₂Has O. In Patent Document 3 or the corresponding US patent (Patent Document 7), the relatively high alkali content is K.₂O and / or Li₂Achieved by using O. However, this has the disadvantage that mixed alkaline effects may appear in the glass composition. This results in a non-linear reactive change. Therefore, the reactivity can no longer be rigorously adjusted.

Patent Document 4 and Patent Document 5 also have Ag in subsequent process steps.₂The glass composition made antimicrobial by O is described. The well-known glass from Patent Document 4 or the corresponding US Patent (Patent Document 8) and Patent Document 5 is B.₂O₃It is a borosilicate glass having a ratio of. Patent Document 5 is further characterized by a relatively low phosphorus content in the glass.

Patent Document 6 describes a glass containing ZnO at a very high concentration (35 to 45 mol% ZnO). This high ZnO concentration has a negative effect on the chemical resistance of the glass. This glass is inadequately stable for long periods of time.

Additional Ag₂In all glass compositions to which O is added, silver is not uniformly distributed because a composite material in which silver or silver ingots are laminated on the surface of the glass phase is formed.

Patent Document 9 describes a soluble glass whose antimicrobial activity is achieved only by adding silver. The glass of Patent Document 9 also has no Zn. This is disadvantageous because zinc synergistically contributes to the desired antimicrobial activity.<patcit num="1"><text>U.S. Pat. No. 5,290,554</text></patcit><patcit num="2"><text>U.S. Pat. No. 6,143,318</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 2001-247333</text></patcit><patcit num="4"><text>Japanese Unexamined Patent Publication No. 2001-247336</text></patcit><patcit num="5"><text>Japanese Unexamined Patent Publication No. 2001-247335</text></patcit><patcit num="6"><text>Japanese Patent Application Laid-Open No. 08-175843</text></patcit><patcit num="7"><text>U.S. Patent Application Publication No. 2001/0023166</text></patcit><patcit num="8"><text>U.S. Patent Application Publication No. 2001/0006987</text></patcit><patcit num="9"><text>Japanese Unexamined Patent Publication No. 04-338129</text></patcit><patcit num="10"><text>International Publication No. 03/0621 163 Pamphlet</text></patcit><nplcit num="1"><text>VDI-Lexikon Werkstoff-Technik (1993), pp. 375-376</text></nplcit><nplcit num="2"><text>Bart Gottenbos et al., Materials in Medicine 10 (1999) pp. 853-855, Oberflaeche von Polymeren</text></nplcit><nplcit num="3"><text>Speier et al., Journal of Colloid and Interface Science 89 pp. 68-76 (1982)</text></nplcit><nplcit num="4"><text>Kenawy et al., Journal of controlled release 50, pp. 145-52 (1998)</text></nplcit><nplcit num="5"><text>European Pharmacopoeia (3rd Edition)</text></nplcit><nplcit num="6"><text>T.Bechert, P.Steinruecke, G.Guggenbichler, Nature Medicine, Vol. 6, No. 8, September 2000, pp. 1053-1056</text></nplcit>

<p> A first object of the present invention is to eliminate the drawbacks of conventional techniques and to provide a glass composition having antimicrobial activity, high chemical resistance and high reactivity.</p><p> A second object of the present invention is to provide a glass composition that is free of alkali but still has sufficient antimicrobial activity or high chemical resistance.</p><p> The antimicrobial action is understood here as a biokilling action or a biostatic action including bacteria, fungi, algae, yeast and the like.</p>

<p> The above-mentioned problems are solved by the glass composition according to claim 1, the glass ceramics according to claim 24, or the glass powder or glass ceramic powder according to any one of claims 25 to 29.</p><p> The antimicrobial phosphate glass of the present invention is Na compared to the glass of the prior art.₂It is characterized by a high proportion of O. Thereby, the improved reactivity is combined with the uniform release of biokill ions, and antimicrobial ions such as Ag or Zn are released very well in these glasses, thus more than in the prior art. High antimicrobial activity is achieved. Another advantage of such glass is over 9.0% Na₂The O content is to lower the Tg of the glass. Tg is understood as the transition temperature of glass as described in Non-Patent Document 1 and the like. This makes it possible to melt the glass at a relatively low temperature.</p><p> In addition, Na₂Since O increases the coefficient of thermal expansion α, the thermal stability with the polymer is improved.</p><p> The glass polymer composite allows at least partial melting into high temperature polymers such as PEEK. In addition to using Na alone, it is also possible to use another alkali such as K or Li.</p><p> The above problem is solved by the broadly alkali-free glass composition according to claim 13, the glass ceramics according to claim 24, or the glass powder or glass ceramic powder according to any one of claims 25 to 29. It will be resolved.</p><p> The compositions of the second aspect of the invention are further characterized in that they are almost tin-free, i.e. Sn-free except for impurities. Sn-containing glass has an undesired coloring because Sn in the glass promotes the reduction of ions to metallic silver of Ag +.</p><p> Further, the plastic glass or glass-ceramic composites according to claims 40 to 43 are preferably used.</p>

In the glass composition of the present invention, Ag₂When introducing O, Ag₂Unlike the conventional technique, O is uniformly dispersed in the glass.

If silver is not present in the glass composition except for impurities, i.e. Ag₂When O = 0% by weight, the glass preferably contains more than 5% by weight ZnO to achieve antimicrobial activity.

This is particularly preferable when silver is not added to the glass in a form that does not exhibit an oxidizing action, for example, as silver nitrate, is not melted under oxidizing conditions, and the coloring of the glass is prevented. This is because such silver-containing glass may be colored by irradiation with light, a redox method, or the like.

The addition of silver leads to the coloring of the glass very often. A mixture that does not oxidize silver, such as silver nitrate (AgNO)₃), Such coloring can be avoided. In addition, this glass is oxidized within the glass and therefore Ag⁺Metal Ag⁰In order to eliminate the reduction to, it is preferably melted under oxidizing conditions such as using oxygen foam. This can also be achieved by tank adjustment, such as by oxidative blast furnace adjustment. By carrying out such a process, when silver is added, neither the coloring of the glass nor the coloring of the polymer in the subsequent processing can be eliminated. Other components such as alkalis and alkaline soils can also be added, preferably as oxidizing components, such as nitrates and peroxides.

Other components such as alkalis and alkaline soils can also be added to the raw material mixture preferably as nitrates.

The total nitrate content is preferably greater than 0.5 or 1.0% by weight, particularly preferably greater than 2.0% by weight, and very preferably greater than 3.0% by weight.

When a strong antimicrobial action with little or no coloring of the glass is required and an oxidizing additive such as nitrate cannot be added to the mixture at the time of melting, a silver concentration of 1% by weight or less is particularly preferable.

In one evolution, in the case of a glass composition containing a small amount of alkali, this glass composition is free of aluminum and no heavy metals other than zinc. The addition of zinc enhances the antimicrobial activity in such glass compositions.

The glass composition or the glass ceramics obtained from the glass ceramics or the glass powders or ceramics powders obtained from the glass compositions have no toxic problems in use in cosmetics and pharmaceuticals, and there are no heavy metals other than Zn.

For use in areas where glass comes into direct contact with humans, especially skin tissue or body fluids, a special composition that is alkali-free and aluminum-free is suitable.

The glass composition or the glass ceramics obtained from it are used to achieve storage of the product itself or to an external antimicrobial effect, i.e. to release antimicrobial agents, especially ions such as zinc or silver.

There should be no toxicity problems with the use of glass compositions or glass ceramics or glass powders or glass ceramic powders to enable the use of antimicrobial / biological effects in products in coloring and lacquer coating, etc. Not a prerequisite. In this case, the composition is Cr₂O₃Or it may contain CuO.

The glass composition or glass ceramics or glass powder or glass ceramic powder of the present invention is used to achieve the preservation and / or external antimicrobial action of the product itself, that is, the antimicrobial action substance, particularly ions such as zinc or silver. Used to release.

Glass or glass ceramics or glass powder or glass ceramic powder can be applied to a polymer as a coating, that is, a protective film when the hydrolysis resistance is sufficiently high.

When the glass composition or glass ceramics or glass powder or glass ceramic powder is used for coloring and lacquer coating in order to utilize the antimicrobial / biological action in the product, there is no toxicity problem. Is not a prerequisite, this composition is Cr₂O₃Or it may contain CuO.

The alkali-free composition is advantageous when used in certain plastics or lacquers under certain conditions where the polymer chains are not broken and thereby the polymer is not locally destroyed.

This confirmed that the mechanical and optical properties of the polymer were not adversely affected.

In particular, polymer chains such as polycarbonate are not attacked, so the mechanical and optical properties of polycarbonate are not adversely affected by the glass powder of the invention as an admixture.

Compared to the well-known silicate glass from the prior art, the phosphate glass described herein is more reactive and therefore has better antimicrobial activity. Moreover, the phosphate glasses described herein have a lower Tg and therefore can be easily processed at relatively low temperatures.

Furthermore, when the glass, which melts at the relatively low temperatures described here, is mixed with the highly melted polymer, the glass melts partially or completely, so that the glass forms an internal bond to the polymer, which is not the case. It leads to very uniform dispersion in the polymer. Melting of glass as described can be achieved, for example, when the polymeric glass composites of the present invention are processed into plastic intermediates or plastic products with biocidal properties. In that regard, it is particularly desirable to refer to melting by extrusion molding of polymer glass composites. This melting increases the antimicrobial activity and achieves higher strength of the polymer glass composite. In addition, the flammability or temperature resistance of this material is increased. No such melting is observed in silicate glass, which is well known from conventional techniques such as Patent Document 10 and can be mixed with plastics. Moreover, the antimicrobial activity of such a mixture is significantly lower than when the glass of the invention is mixed with the plastic.

The glass composition of the present invention further has anti-inflammatory and wound healing properties. This is particularly advantageous when used in the fields of cosmetics and pharmaceuticals.

The alkali-containing glass composition contains the following components in% by weight with respect to the oxide base. P₂O₅ More than 66% by weight, less than 80% by weight SO₃ 0-40% by weight B₂O₃ 0 ~ 1% by weight Al₂O₃ 6.2 by weight over, 80% by weight or less SiO₂ 0 ~ 10% by weight Na₂O 9% by weight or less, 20% by weight or less K₂O 0 ~ 25% by weight CaO 0 ~ 25% by weight MgO 0 ~ 15% by weight SrO 0 ~ 15% by weight BaO 0 ~ 15% by weight ZnO&gt; 0% by weight, 25% by weight or less Ag₂O 0 ~ 5% by weight CuO 0 ~ 10% by weight GeO₂ 0 ~ 10% by weight TeO₂ 0 ~ 15% by weight Cr₂O₃ 0 ~ 10% by weight J 0 ~ 10% by weight F 0 ~ 3% by weight

Na₂The content of O is preferably more than 9.5% by weight, particularly preferably more than 10% by weight, and very preferably more than 10.5% by weight. A highly preferred embodiment is Na&gt; 11% to 11.5% by weight.₂Including O.

When the alkali-containing glass composition contains Na, it is preferably free of Li and K except for impurities.

In the second embodiment of the present invention, the alkali-free glass composition contains the following components in weight% by weight relative to the oxide base. P₂O₅ More than 66% by weight, less than 80% by weight SO₃ 0-40% by weight B₂O₃ 0 ~ 1% by weight Al₂O₃ 0 ~ 3.9% by weight SiO₂ 0 ~ 10% by weight CaO 0 ~ 25% by weight MgO 0 ~ 15% by weight SrO 0 ~ 15% by weight BaO 0 ~ 15% by weight ZnO 1 ~ 25% by weight Ag₂O 0 ~ 5% by weight CuO 0 ~ 10% by weight GeO₂ 0 ~ 10% by weight TeO₂ 0 ~ 15% by weight Cr₂O₃ 0 ~ 10% by weight J 0 ~ 10% by weight F 0 ~ 3% by weight

In that case, the total alkali content is less than 0.4% by weight, preferably less than 0.1% by weight, very preferably less than 0.01% by weight, and this composition is almost Sn-free except for impurities.

The glass or glass ceramics or glass powders of the present invention obtained starting from the glass composition described above have surprisingly sufficient chemical resistance, high reactivity and neutral values to pH to the skin in the composition range described. The sex value was confirmed. This glass, especially glass powder, has a biokilling effect, at least a biostatic effect. Based on the neutral value or pH neutral value for the skin in an aqueous solution, the glass or the glass powder obtained from it or the glass ceramics obtained from it or the glass ceramic powder obtained from it harmonizes with the skin in contact with humans. To do. Furthermore, this glass has no toxicity problems. The load of heavy metals is preferably less than 20 ppm for Pb, less than 5 ppm for Cd, less than 5 ppm for As, less than 10 ppm for Sb, less than 1 ppm for Hg, and less than 10 ppm for Ni. When in contact with water, in the glass of the present invention, ion exchange such as Na ion or Ca ion occurs between the glass surface and the liquid medium. P that forms glass, that is, forms a mesh₂O₅By changing the components, the reactivity or dissolution rate can be adjusted. The degree of liberation of killing ions can be regulated by ion exchange and glass melting. In order to obtain the chemical resistance of the glass on demand, that is, to obtain hydrolysis resistance that is not too low, the alkali-containing glass is made of Al.₂O₃Is preferably contained at a concentration of more than 6% by weight. Preferably the Na / Al ratio is 2: 1 to 1: 1% by weight. Na and Al contribute to the composition of the glass network in a molar ratio of 1: 1. And excess Na acts as a network modifier. Therefore, the reactivity of the glass can be directly adjusted by the Na / Al ratio.

Alkali-containing glass composition, Na₂By properly introducing O and CaO, Na₂High O content loosens the network and thus facilitates the release of introduced biocidal ions such as Zn, Ag, which can stop network formation and regulate the reactivity of the glass. it can. Glass matrix is Na₂When O is contained alone, more than 10% by weight of Na₂O content is particularly preferred, and Na₂Na in the introduction of O and CaO₂O&gt; 5% by weight and CaO&gt; 5% by weight were found to be particularly preferred.

In the case of alkali-free glass compositions, proper introduction of network-modified alkaline earth ions will loosen the network at high alkaline earth contents, thus resulting in introduced biokilling ions such as Zn. Since it is easily released, reticulation can be stopped and the reactivity of the glass can be regulated.

The pH value can be adjusted to a neutral value for the skin by ion exchange of Na ions or Ca ions in the aqueous solution and the OH group of phosphor oxide that does not contribute to the formation of the glass network. The proportion of OH groups in phosphoroxide that does not contribute to glass network formation is determined on the one hand by the composition of the mixture, and on the other hand is affected by melting parameters such as melting time and the purity of the raw material.

With a glass composition that is not alkaline-free, Na₂O content and CaO content, P₂O₅By appropriately adjusting the OH groups of phosphoroxides that do not contribute to the content or glass network composition, the pH value of the glass in contact with water can be changed by changing the glass composition or by changing the melting parameters. It can be adjusted strictly by this. Adjustments over a wide pH range of 4.0-7.0 are achieved.

For glass compositions without alkali, the CaO content, P₂O₅By appropriately adjusting the OH groups of phosphoroxides that do not contribute to the content or glass network composition, the pH value of the glass in contact with water can be changed by changing the glass composition or by changing the melting parameters. It can be adjusted strictly by this. Adjustments over a wide pH range of 4.0-8.5, particularly preferably 4.5-7 are achieved.

Glasses containing a proportion of CaO greater than 5% by weight are particularly preferred, as Ca performs a special function. In the presence of Ca, the glass can be bioactive. This biological activity is characterized in that a mineral film, a so-called hydroxyapatite film, is formed on the surface of the particles. This membrane closely resembles the hard tissue of human tissue and therefore fits very well into both hard and soft tissue.

If there is a glass composition in which the antimicrobial activity of the glass is caused by ions such as zinc or a small amount of silver, then in alkali-containing glass this antimicrobial activity is further enhanced by free alkaline ions such as Na, K or alkaline soil. Alkali-free glass is promoted by alkaline earth ions such as Ca or Ba. Antimicrobial effects appear because the osmotic equilibrium of cells is disrupted. In a highly preferred embodiment, the glass composition comprises Ca and Zn in a ratio of 1: 1 to 1: 2 by weight. For example, this is achieved by an embodiment comprising 8% by weight CaO and 8.5% by weight ZnO.

This preferred embodiment containing Ca and Zn in a ratio of 1: 1 to 1: 2 has the desired antimicrobial activity on the one hand and is particularly "biocompatible" on the other hand, i.e. in particular contact with body tissue. It is characterized by conforming to.

Embodiments of the present invention, characterized by being non-toxic, are particularly suitable for use in creams or lotions for application to the skin or similar offerings.

In the medical field, reduction or avoidance of skin inflammation such as skin erythema and irritation in the cosmetic and medical fields, and wound care are potential uses.

Another area of application is food preservation.

For applications in fields where glass, glass ceramics or glass powder or glass ceramic powder obtained from it come into contact with humans, such as in fields such as medicine and beauty, glass preferably does not contain another heavy metal. In such applications, preferably particularly pure raw materials are used.

The biokilling or biostatic action of the glass of the present invention or the glass powder obtained from it or the glass ceramic of the present invention obtained from this starting glass is caused by the liberation of ions in a liquid medium, especially in water. Glass or the glass powder and glass ceramics obtained from it show a killing effect on bacteria, fungi, and viruses. This effect is due in particular to the presence of zinc.

For use in fields that do not come into direct contact with humans, the glass or glass powder or glass ceramics of the present invention can also contain heavy metal ions in relatively high concentrations in order to achieve a particularly strong biokilling effect. Such heavy metal ions are Ag, Cu, Ge, Te and Cr. The glass or glass powder or glass ceramics of the present invention can be added to polymers, paints and lacquers.

A preferred field of use for the glass of the present invention or the glass ceramics obtained from it, glass powder or glass ceramic powder is its use in polymers to achieve biokilling or biostatic action. On the one hand, the preservation of the polymer itself is central, that is, to protect the polymer from bacterial and fungal pathogenesis. In addition, it can create a biostatic or biotoxic polymer surface, in which case as much non-biological material as possible, such as ions, is released to the surroundings. Another object is to provide a polymer that specifically liberates biokilling substances.

Therefore, in another aspect of the invention, a plastic glass composite is provided that includes: -Plastic material -Based on the alkali-containing or alkali-free glass composition described above -Glass and / or glass ceramics

Surprisingly, it has been found that in a preferred embodiment of the invention, strong antimicrobial activity is achieved when using alkali-free glass, even in the absence of alkali in the glass matrix. The amount of alkaline ions usually regulates the reactivity of glass, so the intensity of antimicrobial activity can be regulated both temporally and quantitatively. The alkali-free glasses described herein can be adjusted to various reactivity without alkali ions. In the alkali-free glass of the present invention, the alkaline earth of the glass becomes the aqueous medium H due to the reaction on the glass surface.⁺Exchange for ions. By adding an antimicrobial action ion such as Zn, the antimicrobial action of the glass composition can be further enhanced. Therefore, in the glass composition or glass ceramic composition of the present invention, the antimicrobial action can be regulated by changing the alkaline earth content and also by the antimicrobial action zinc itself.

Since glass ceramics or glass powders or glass-ceramic powders of such glass compositions in alkali-free glass compositions or polymers, as well as those containing alkalis, are encapsulated by the polymer. It is expected that this is of insufficient antimicrobial properties based on the shielding of the aqueous medium. Surprisingly, but with the addition of very small amounts of Ag and / or another biokill ion such as Zn, Cr, Cu, the glass, glass ceramics, glass powder or glass ceramic powder in the polymer matrix is significant. It was found that antimicrobial activity appears.

This means that silver ions and / or other biokilling ions are already "activated" in the glass matrix with a very small amount of water in the polymer produced by the conventional method, thus for a long time. It is surprising because it is sufficient to achieve the antimicrobial activity of.

Heating a polymer glass composite containing such a glass composition, glass ceramics, glass powder or glass ceramic powder causes the glass to partially melt according to the respective adjusted processing temperatures, thereby increasing antimicrobial activity. Other properties of the composite, such as strength, are also positively affected.

In one evolution of the invention, the glass composition also includes Ca and Zn, and the total amount of CaO and ZnO is planned to be in the range of 5-40% by weight in this glass composition. Preferably, the amount of ZnO in this total amount exceeds 0.1% by weight, preferably more than 1% by weight.

As described above, the glass having the composition of the present invention or the glass ceramics, glass powder or glass ceramic powder obtained from the glass exhibits a biostatic or biokilling action in the polymer. It can be used to preserve the polymer, especially to protect it from bacterial disease or bacterial destruction. It is also conceivable that the polymer will have an antimicrobial surface. Such antimicrobial surfaces are designed to minimize the release or release of antimicrobial agents, especially ions, to the outside, i.e. to the outside of the polymer surface.

The glass of the present invention also allows antimicrobial action ions to slowly release from the polymer matrix, especially in the absence of alkali.

In that case, the water content of the polymer and the diffusion of ions moving in the polymer matrix play important roles. Generally, here, the amount of biokill ions in the glass matrix or the glass concentration in the polymer is also higher than that in the above-mentioned utilization. This release can be associated with partial or complete melting of the glass. In a particularly preferred embodiment, the polymer matrix is also partially or completely melted. This is especially the case when the polymer matrix is water soluble.

In one evolution of the invention, the glass, the glass ceramics obtained from it, and the glass powder or glass ceramic powder obtained from it are not only included in the polymer itself if hydrolysis resistance is sufficient, but also a coating, i.e. It is intended that it can be applied to polymers as a protective film.

To ensure compatibility with the polymer and regulate reactivity, the amount of CaO is preferably greater than 1% by weight, preferably greater than 7.7% by weight. Another advantage of CaO content above 1% by weight is that it increases the temperature tolerance of the glass.

Another area of use of glass described herein is its use in paints and lacquers. The purpose is to preserve the paint and / or to achieve an external achievement of the biokilling / biostatic membrane or biokilling action, such as by damage to the moldy surface.

Based on the high phosphorus content, the glass, glass powder, glass ceramics or glass ceramic powders of the present invention have a bioactive effect in addition to the bioactive effect by ion exchange or ion liberation. The glass, glass ceramics, glass powder or glass ceramic powders of the present invention are therefore particularly biocompatible, i.e. particularly compatible with body tissue.

In a preferred embodiment, the amount of heavy metals can be reduced by substituting Zn entirely or partially preferably with Ca, but also with Mg. Such substances ensure good environmental compatibility.

In the glass, glass powder, glass ceramics or glass ceramic powder of the present invention, ions are exchanged or liberated by a reaction on the glass surface or local melting of the glass. Therefore, the antimicrobial effect is particularly due to the release of ions. The antimicrobial action of ion exchange or ion release slows cell growth.

The antimicrobial glass surface incorporated into the system also plays a role other than release. The antimicrobial action on the glass surface is also due to the presence of antimicrobial action ions. However, it is also well known that the surface charge, i.e. the zeta potential of the powder, can have antimicrobial activity, especially for Gram-negative bacteria. Positive surface charges attract bacteria, but Gram-negative bacteria do not grow on surfaces with positive zeta potential, i.e. cannot grow, so antimicrobial activity begins with a positive surface charge on Gram-negative bacteria. .. In this regard, it is desirable to refer to Non-Patent Document 2.

The antimicrobial action in powders having a positive surface charge is described in Non-Patent Document 3 and Non-Patent Document 4. Forming glass, i.e. forming a mesh P₂O₅By changing the composition, the melting rate of the glass can be adjusted. The degree of liberation of killing ions can be regulated by ion exchange and glass melting.

In particular, the release of phosphate in aqueous solution allows the pH value to be adjusted appropriately, especially to a neutral value for the skin.

Na on alkali-containing glass like ZnO or CaO₂High Na with proper introduction of O₂At the amount of O, the network becomes loose, and thus the introduced biokilling ions such as Zn and Ag are easily released, so that the network formation is stopped and the reactivity of the glass is regulated. In alkali-free glasses, reactivity is controlled by the proper introduction of CaO or ZnO. Proper introduction of alkaline earth ions such as CaO or ZnO will loosen the network at high CaO levels and thus facilitate the release of introduced biokilling ions such as Zn, Ag, resulting in network formation. Stop and regulate the reactivity of the glass. Since the glass becomes biologically active in the presence of Ca, the glass of the present invention containing CaO having a weight portion exceeding 5% by weight is particularly preferable. A particularly preferred embodiment comprises Ca and Zn in a ratio of 1: 1 to 1: 2% by weight.

The pH value can be adjusted to a neutral value such as pH = 7 by ion exchange of Na ion or Ca ion in an aqueous solution. P₂O₅If the glass network changes due to an increase in the amount, melting parameters such as melting time, purity of the raw material, etc., for example, the ratio of free OH groups in phosphor oxide changes, the environment may shift to a weakly acidic environment. As it can occur, it produces a neutral pH value for the skin at pH = 5.5.

Network formation component P₂O₅Na for quantity₂By appropriately adjusting the amount of O and the amount of CaO, the pH value of the glass in contact with water can be strictly adjusted by changing the glass composition. Adjustments over a wide pH range of 4-8 are achieved.

The killing or biostatic action of the glass of the present invention or the glass powder obtained from it or the glass ceramic or glass ceramic powder of the present invention obtained from this starting glass is caused by ion liberation in a liquid medium, particularly in water. Glass or the glass powder and glass ceramics obtained from it have a killing effect on bacteria, fungi and viruses.

From the glass described here, glass ceramics or ceramics can be obtained. It is subsequently manufactured by performing a forging step on an intermediate material (such as a glass strip or ribbon) or a product such as glass powder or fiberglass. Following this forging step, new milling may be required to adjust to the desired particle size.

Using the grinding process, the glass composition is ground into glass powder with a particle size of less than 100 μm. A particle size of less than 50 μm to less than 20 μm was found to be appropriate. Particle sizes less than 10 μm and less than 5 μm are particularly suitable. Particle sizes less than 2 μm were found to be very well suited.

This milling process can be carried out either by drying or by using a water-insoluble milling medium or a water-soluble milling medium.

Different glass powders of composition ranges with different compositions and particle sizes can be mixed to combine specific effects.

A pH value of 4.0-8.0 is achieved, depending on the particle size, concentration and composition of each powder.

Mixing of glass powders with different compositions and particle sizes can be synergistically combined to adjust the special properties of the individual glass powders. Therefore, for example, it is possible to control the antimicrobial action of the glass powder by the particle size.

This glass powder glass is P as a mesh-forming body.₂O₅In that case, the degree of bridging is particularly susceptible to melting parameters.

Na₂O is added as a flux in alkali-containing glass when the glass melts. At concentrations less than 5% by weight, melting behavior is negatively affected. Moreover, the mechanisms required for ion exchange are no longer sufficient to achieve antimicrobial activity. Na higher than 30% by weight₂At O concentrations, the chemical resistance is too low or the reactivity is too high. Furthermore, the melting behavior is negatively affected.

Alkali-containing glass requires alkali oxides and alkaline earth oxides to form a glass network. The proportion of alkaline oxides and alkaline earth oxides in the glass composition allows the glass to be conditioned on the desired reactivity of the glass.

Alkali-free glass requires alkaline earth oxides to form a glass network. The desired reactivity of the glass can be adjusted by the proportion of alkaline earth oxides in the glass composition.

Glasses of the invention containing CaO having a weight portion of more than 5% by weight are particularly preferred, as the glass is particularly compatible with body tissue in the presence of Ca.

Al₂O₃The amount increases the chemical resistance of crystallization stability and helps control antimicrobial activity. This also contributes in part to the composition of the glass mesh. Al₂O₃Is added in excess of 6.2% by weight to the alkali-containing glass composition in a preferred embodiment. Alkali-containing glass has less than 6.2% Al₂O₃In the case of amounts, the reactivity is too high, i.e. the glass dissipates too quickly and therefore the long-term effect on the release of antimicrobial ions is not achieved.

Very low Al less than 3.9% by weight for alkali-free glass₂O₃Surprisingly, a long-term effect on the release of antimicrobial ions is achieved because the amount increases the reactivity of the alkali-free glass. Therefore Al₂O₃Depending on the amount, a long-term effect on the release of antimicrobial ions is achieved in both alkali-containing and alkali-free glasses.

ZnO is an important component for high temperature moldability of glass. This improves crystallization stability and increases surface tension.

ZnO has antimicrobial properties and is used in a preferred embodiment of the invention to achieve antimicrobial activity, i.e. preferably in a composition free of other heavy metals except zinc.

In addition, it can reduce inflammation and promote the effect of healing wounds. Up to 20% by weight ZnO can be included to achieve the effect of suppressing inflammation and healing wounds. Preferred embodiments include more than 10% by weight ZnO or more than 12% by weight ZnO. For pure glass with antimicrobial activity, the glass matrix can also be constructed without zinc. Instead of Zn, this glass preferably contains Ca. In this case, the antimicrobial effect is achieved by the killing ions such as Ag, Te, Ge, Cr and Cu introduced into the glass matrix. The substance that fits it is Ag₂O or CuO.

In addition to being introduced directly into the glass matrix during the melting process, this ion can also be introduced only into the glass surface region by ion exchange.

Ag₂O and CuO can be added as antimicrobial action additives to enhance the antimicrobial action of the basic glass.

The glass of the present invention does not cause skin irritation.

The combination of pH action, surface effect action, and Ag, Cu or Zn release achieves a significant increase in antimicrobial action far beyond the sum of the individual actions. The free Ag, Cu, Zn ion concentration in the product is clearly less than 1 ppm in this case.

In that case, Ag, Cu, and Zn can be introduced by the salt corresponding to the melting, or by ion exchange of the glass after melting.

Fe to achieve color effect, such as when used in paints and lacquers₂O₃, CoO, CuO, V₂O₅, Cr₂O₅Single or multiple color-giving components, such as, are added to the glass in a total concentration of less than 4% by weight, preferably less than 1% by weight.

Glass, glass powder, glass ceramics or glass ceramic powder having a composition within the required composition range are used in the fields of sanitary papers, cosmetics, paints, lacquer, mortar, pharmaceuticals, beauty applications, food additives, as well as deodorizing products and controls. For use in sweat agents, as well as products for the treatment of skin inflammation, acute and chronic wounds, and dental products such as tooth care / tooth hygiene and oral hygiene / oral hygiene and tooth filling, crowns, inclusions, etc. Satisfy all requirements regarding the use of.

Each glass powder can be used in a suitable form. It is also possible to mix different glass powders with different composition ranges with different compositions. It is also possible to mix with other glass powders to combine specific effects.

Ingredients such as fluorine can be added to the glass up to a total concentration of 5% by weight, depending on the field of application. In addition to its antimicrobial and anti-inflammatory properties, this embodiment has been found to be used especially in the areas of tooth cleaning and tooth hygiene, as it allows the release of fluorine, which hardens enamel, in small concentrations. Is done.

A particularly preferred use in the dental field is to use the described glass in dental products. It is particularly suitable to use the glass of the present invention alone or in combination with other materials for tooth filling, crowns and inserts. In this case, it is particularly preferable to use the glass or glass ceramics of the present invention and the glass powder or glass ceramic powder obtained from them as a composite material with a polymer substance.

The use of the described glass in the polymer field is not limited by this, and there are polymers particularly suitable for the addition of bioglass. This is especially PMMA, PVC, PTFE, PEEK, polystyrene, polyacrylic acid ester, polyethylene, polyester, polycarbonate, PGA biodegradable polymer, LGA biodegradable polymer or biopolymer collagen, fibrin, chitin, chitosan, polyamide, Polycarbonate, polyester, polyimide, polyurea, polyurethane, organic fluoropolymer, polyacrylamide and polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyolefin, polystyrene and styrene copolymer, polyvinyl ester, polyvinyl ether, polyvinylidene chloride , Vinyl polymer, polyoxymethylene, polyaziridine, polyoxyalkylene, synthetic resin or alkyl resin, amino resin, epoxy resin, phenol resin or unsaturated polyester resin, conductive polymer, high temperature polymer, inorganic polymer, polyphenyl Biopolymers such as oxide silicones, celluloses, cellulose esters, cellulose ethers, enzymes, gelatins, natural resins, nucleic acids, polysaccharides, proteins, silk threads, starches or wool.

Preferably, the glass of the present invention has a small amount of alkali in use with an alkali sensitive polymer such as polycarbonate, or in a preferred embodiment there is no alkali.

In particular, it is suitable for use in the following products, such as as an antimicrobial additive in polymers.

That is, Cutting plate, gloves, Garbage can, Knife grip, Tableware, such as chopsticks, tablet, table cloth, Textile fibers,

refrigerator, Automatic dishwasher, Laundry dryer, Washing machine, phone, keyboard, Iron, rice cooker,

handle, Automobile instrument, Armrest, key, Door handle, ashtray, Shift lever, switch,

Ballpoint pen, Floppy (registered trademark) disk, Audio video cassette, Compact disc (CD), Clipboard.

Further, such glass, glass ceramics, glass powder, or glass ceramic powder is also found to be used as an additive in the clothing industry, preferably to chemical fibers.

That is, clothing, socks, underwear, handkerchief, Toilet towel, Wall cloth, Pillowcase, Pillow stuffing, Swimsuit, It may be used for swimming caps.

The glass of the present invention, the glass ceramics of the present invention, and other chemical fiber-based or polymer-based products that can include glass powders or glass ceramic powders obtained therein.

Floor carpet, contact lens, Contact lens holder container, Playground sand, Plastic coins, bill, toy, Watches, Diving suit.

Antimicrobial glass powder is particularly suitable as an additive to fibers, especially for use in fibers for floor carpets.

The glass described in the present invention or the glass ceramics obtained from it, or the glass powder or the glass ceramic powder obtained from the glass obtained by grinding is water-soluble, but has sufficient chemical resistance. The glass or glass powder first acts by ion exchange or ion release, which is associated with surface reactions and metal ion release.

Surprisingly, the glass powders or glass ceramic powders of the present invention are highly reactive and have higher antimicrobial activity than the bioactive glass described in the prior art or the group of glass powders made from such glass. Is shown.

Hereinafter, the present invention will be described in detail based on examples.

First, the composition of alkali-containing glass having an antimicrobial effect will be described. From the raw material, the glass was melted in a platinum crucible and then processed into a ribbon. The ribbon was further processed into a powder with a particle size of d50 = 4 μm using dry grinding.

Table 1 shows the composition and properties of glass that can be pulverized into the glass powder of the present invention and has an antimicrobial effect. This composition relates to a synthetic value in% by weight relative to the oxide base.

<tables num="1"><img file="JP4602320B2_D0001.tif" /></tables>

Table 2 shows the pH value and conductivity after 60 minutes in a 1 wt% aqueous suspension of the glass powder having the compositions of Examples 1 and 2 in the table below.

<tables num="2"><img file="JP4602320B2_D0002.tif" /></tables>

The antimicrobial action in Example 2 of Table 1 is shown in Table 3. A 0.001 wt% aqueous suspension of glass powder having a particle size d50 = 4 μm of Example 2 was measured. A value of 0 indicates, for example, that the bacteria are no longer present in the suspension relative to the initial starting value of the 260000E.coli bacterium, that is, the antimicrobial effect of this glass powder killed all colony forming units.

<tables num="3"><img file="JP4602320B2_D0003.tif" /></tables>

For the glass powder having a particle size d50 = 4 μm in the glass composition of Example 2 in Table 1, a pH value of 5.1 was confirmed in a 1% weight aqueous solution.

In particular, the glass composition of Example 3 in Table 1 represents a particularly preferred form as it exhibits neutral pH values associated with antimicrobial and anti-inflammatory effects as well as special compatibility with body tissues.

The antimicrobial activity of different alkali-containing glass powders having a particle size d50 of 4 μm and having the glass compositions of Examples 1, 2 and 7 of Table 1 of the growth test is shown below.

In the growth test, a test method for quantifying the effect of the antimicrobial surface becomes a problem. In doing so, simply speaking, the surface antimicrobial effect characterizes how and how much daughter cells are released into the surrounding medium. The implementation of the test is described in Non-Patent Document 6.

This glass powder was uniformly introduced into various polymers. The polymers used were polypropylene (PP), acrylonitrile butadiene styrene (ABS) and polyamide PA.

Since the glass used was adjusted to a pH value from neutral to acidic, the chain termination reaction normally induced in the presence of alkali could be adequately suppressed here in the polymer.

Staphylococcus epidermidis was used as the pathogen. Bacteria present on the skin are important for this pathogen.

Growth observed for 48 hours or longer was observed for a glass powder having a particle size d50 of 4 μm and a glass composition of Example 1 in Table 1, which was uniformly introduced into polypropylene (PP) at the respective concentrations (% by weight) listed. It is shown in Table 4. The starting OD is understood as the optical density in the surrounding medium. Proliferation (formation of daughter cells) and release of cells from the surface into the surrounding medium reduces the permeability of the medium. This absorption at specific wavelengths is associated with surface antimicrobial activity. The higher the starting OD value, the stronger the antimicrobial effect on the surface. The definition of OD magnitude is for all the tables below.

<tables num="4"><img file="JP4602320B2_D0004.tif" /></tables>

Growth observed for 48 hours or longer was observed for a glass powder having a particle size d50 of 4 μm and a glass composition of Example 7 in Table 1, which was uniformly introduced into polypropylene (PP) at the respective concentrations (% by weight) listed. It is shown in Table 5.

<tables num="5"><img file="JP4602320B2_D0005.tif" /></tables>

A glass powder having a particle size d50 of 4 μm and a glass composition of Example 1 in Table 1 which was uniformly introduced into acrylonitrile butadiene styrene (ABS) at the respective listed concentrations (% by weight) was observed for 48 hours or more. The proliferation is shown in Table 6.

<tables num="6"><img file="JP4602320B2_D0006.tif" /></tables>

A glass powder having a particle size d50 of 4 μm and a glass composition of Example 2 in Table 1 which was uniformly introduced into acrylonitrile butadiene styrene (ABS) at the respective listed concentrations (% by weight) was observed for 48 hours or more. The proliferation is shown in Table 7.

<tables num="7"><img file="JP4602320B2_D0007.tif" /></tables>

The growth observed for 48 hours or more with respect to the glass powder having the glass composition of Example 1 in Table 1 having a particle size d50 of 4 μm and uniformly introduced into the polyamide (PA) at the respective concentrations (% by weight) listed. It is shown in Table 8.

<tables num="8"><img file="JP4602320B2_D0008.tif" /></tables>

Growth observed for 48 hours or longer was observed for a glass powder having a particle size d50 of 4 μm and a glass composition of Example 2 in Table 1, which was uniformly introduced into polyamide (PA) at the respective concentrations (% by weight) listed. It is shown in Table 9.

<tables num="9"><img file="JP4602320B2_D0009.tif" /></tables>

Hereinafter, the present invention relating to alkali-free glass will be described in detail based on examples.

The alkali-free glass described can also be produced by the sol-gel process, in addition to the usual melting process.

This alkali-free glass was melted from a raw material in a platinum crucible and then processed into a ribbon. The ribbon was further processed into a powder with a particle size of d50 = 4 μm using dry grinding.

Table 10 shows the composition and properties of the alkali-free glass in the glass powder of the present invention. This composition relates to a synthetic value in% by weight relative to the oxide base.

<tables num="10"><img file="JP4602320B2_D0010.tif" /></tables>

The antimicrobial activity of Example 1 in Table 10 is shown in Table 11. A 0.001 wt% aqueous suspension of glass powder having a particle size of d50 = 4 μm in Example 1 was measured.

<tables num="11"><img file="JP4602320B2_D0011.tif" /></tables>

The antimicrobial activity of Example 2 in Table 10 is shown in Table 12. A 0.01 wt% aqueous suspension of glass powder having a particle size of d50 = 4 μm in Example 2 was measured.

<tables num="12"><img file="JP4602320B2_D0012.tif" /></tables>

The antimicrobial activity of a glass powder having a particle size d50 of about 4 μm and having the glass composition of Example 1 in Table 10 in the growth test is shown below.

In the growth test, a test method capable of quantifying the effect of the antimicrobial surface is particularly preferable. In doing so, simply speaking, the surface antimicrobial effect characterizes how and how much daughter cells are released into the surrounding medium. The implementation of the test is described in Non-Patent Document 6.

This glass powder was uniformly introduced into the polymer.

Staphylococcus epidermidis was used as the pathogen. Bacteria present on the skin are important for this pathogen.

For a glass powder having a particle size d50 of 4 μm and the glass composition of Example 1 uniformly introduced into acrylonitrile butadiene styrene (ABS) and polystyrene (PS) at the respective concentrations (% by weight) listed, 48 hours or more. The observed growth is shown in Tables 13-14 for the various polymer types. The starting OD is understood as the optical density in the surrounding medium. Proliferation (formation of daughter cells) and release of cells from the surface into the surrounding medium reduces the permeability of the medium. This absorption at specific wavelengths is associated with surface antimicrobial activity. The higher the starting OD value, the stronger the antimicrobial effect on the surface.

<tables num="13"><img file="JP4602320B2_D0013.tif" /></tables>

<tables num="14"><img file="JP4602320B2_D0014.tif" /></tables>

<tables num="15"><img file="JP4602320B2_D0015.tif" /></tables>

The phosphate glass composition of the present invention presents for the first time a glass composition having a long-term antimicrobial activity. In particular, glass powders or glass ceramic powders of such glass compositions also exhibit antimicrobial activity when introduced into a polymer matrix.

In addition, polymer glass composites comprising such glass compositions are shown that are characterized by high antimicrobial activity as well as high resistance. Such polymer glass composites made by mixing the polymer with the glass powder to yield a polymer glass powder mixture are particularly preferred. The polymer glass powder mixture is then subjected to heat treatment, such as heating to a temperature in the range of +50 to +350 ° C., while mechanically mixing the polymer glass powder mixture in the mixer. The plastic glass composite is then partially meltable, creating an internal bond between the glass and the particularly highly fused polymer so that the glass is very evenly dispersed in the polymer. become.

The resulting plastic glass composite can be further processed into granules or the like by pulverization, or directly into a plastic intermediate or final plastic product by injection or the like.