JP2006057161A - Antibacterial member, antibacterial leather material and method for producing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antibacterial member which can suppress the propagation of various germs and further can suppress the generation of odor. <P>SOLUTION: The antibacterial member is obtained by allowing a carbon material to coexist at least on a part of the surface in a non-conductive base material and precipitating silver 38 over the surface of the carbon material. Since the carbon material coexists in the antibacterial member, electrolytic treatment can be performed in such a manner that the nonconductive base material is made into the conductive one, and it is also possible that the silver 38 in an electrolytic solution is precipitated by the electrolytic treatment, and by the germicidal action of the silver 38, an antibacterial action can be imparted thereto. Further, the carbon material has an action of adsorbing odor and can suppress the generation of unpleasant odor. Further, powdery silica gel can be coexisted in addition to the carbon material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an antibacterial member, an antibacterial leather material, and a production method for producing these, which can suppress the propagation of various bacteria and the generation of odor.

  In order to give an antibacterial action to a metal member, for example, a base material made of aluminum or an alloy thereof is used as a metal nitrate in a sulfuric acid bath, an oxalic acid bath, or a mixed bath thereof, such as silver nitrate or copper nitrate, or sulfate. Electrolytic treatment in an electrolytic solution to which silver sulfate or copper sulfate is added, thereby forming an anodic oxide film on the surface of the base material, and at the same time, depositing the added nitrate or sulfate metal on the anodic oxide film There exists a processing method (for example, patent document 1). By treating with this surface treatment method, a metal (for example, silver) can be deposited on an anodized film formed on aluminum or an aluminum alloy, and the matrix can have an antibacterial action. .

JP 2002-47596 A

  However, this surface treatment method requires that the base material has conductivity. For example, when the base material is a non-conductive member such as a cloth member, the surface treatment method is used directly on the cloth member. Even so, a metal such as silver cannot be deposited on the cloth member itself, and the cloth member cannot have antibacterial properties.

An object of the present invention is to provide an antibacterial member having an antibacterial property due to silver by precipitating silver even in a non-conductive base material.
Another object of the present invention is to provide a method for producing an antibacterial member having antibacterial properties due to silver by surface treatment.

The antibacterial member according to claim 1 of the present invention is characterized in that a carbon material is mixed in at least a part of the surface of a non-conductive base material, and silver is deposited on the surface of the carbon material.
In the antibacterial member according to claim 2 of the present invention, an aluminum material is mixed in at least a part of the surface of the non-conductive base material, and silver is deposited on the anodized film formed on the surface of the aluminum material. It was made to be characterized.

In the antibacterial member according to claim 3 of the present invention, the base material is a cloth member, a leather member, or a foamable resin member.
In the antibacterial member according to claim 4 of the present invention, silica gel is further mixed in at least a part of the surface of the base material.

  Moreover, in the antibacterial leather material according to claim 5 of the present invention, the surface of the leather member is mixed with the aluminum material by performing a tanning treatment using a tanning agent containing the aluminum material, and formed on the surface of the aluminum material. Silver is deposited on the anodized film thus formed.

  Further, in the antibacterial leather material according to claim 6 of the present invention, the surface of the leather member is mixed with a carbon material by performing a tanning treatment using a tanning agent containing a carbon material, and silver is formed on the surface of the carbon material. It is characterized by having precipitated.

In the antibacterial leather material according to claim 7 of the present invention, silica gel is further mixed on the surface of the leather member.
In the method for producing an antibacterial member according to claim 8 of the present invention, a non-conductive base material mixed with a carbon material is mixed with silver nitrate or silver sulfate in a sulfuric acid bath or an oxalic acid bath or a mixed bath thereof. In an electrolytic solution to which a mixture of silver nitrate and silver sulfate was added, either an AC / DC superimposed current, an AC current, a PR current that passed a negative wave, or a pulse wave that passed a negative wave was added to perform electrolytic treatment, and the added Silver nitrate or silver sulfate is deposited on the surface of the carbon material.

  In the method for producing an antibacterial member according to claim 9 of the present invention, a non-conductive base material mixed with an aluminum material is mixed with silver nitrate or silver sulfate in a sulfuric acid bath or an oxalic acid bath or a mixed bath thereof. In an electrolytic solution to which a mixture of silver nitrate and silver sulfate is added, either an AC / DC superimposed current, an AC current, a PR current that flows a negative wave, or a pulse wave that flows a negative wave is applied to perform electrolytic treatment, whereby the aluminum An anodic oxide film is formed on the surface of the material, and simultaneously added silver nitrate or silver sulfate silver is deposited on the anodic oxide film.

  According to the antibacterial member of the first aspect of the present invention, the carbon material is mixed in at least a part of the surface of the non-conductive base material. Since carbon has conductivity, the base material can be made conductive by mixing the carbon material with the base material. And silver can be deposited on the carbon material mixed in the base material by performing a predetermined electrolytic treatment on such a base material. The silver thus deposited has an antibacterial action. In particular, when the antibacterial member is in a high humidity environment, the precipitated silver is ionized and released to the surroundings, and the released silver ions exhibit a stronger antibacterial action. Thus, a desired antibacterial effect can be obtained. Therefore, when silver ions are released in this way, their strong antibacterial action significantly reduces the growth of germs even on the skin surface where the germs are easily steamed due to secretions such as sweat and fat. Thus, it is possible to suppress the occurrence of skin irritation, itching and the like. Further, since the number of germs is reduced, there is almost no odor due to the breeding, and the generation of odor can be suppressed.

  This silver deposition may be at least part or all of the surface of the carbon material. Furthermore, since carbon has a property of adsorbing odors, generation of unpleasant odors due to various bacteria can be suppressed. The antibacterial member is used so that the antibacterial member is brought into contact with or in close contact with a portion where skin surface irritation or the like is likely to occur.

  Moreover, according to the antibacterial member according to claim 2 of the present invention, the aluminum material is mixed in at least a part of the surface of the non-conductive base material. Since aluminum has conductivity, the base material can be made conductive by mixing an aluminum material. Then, by subjecting such a base material to a predetermined electrolytic treatment, an anodized film can be provided on the surface of the aluminum material mixed in the base material, and silver can be deposited on the anodized film. The antibacterial action of silver can suppress the propagation of germs and suppress the occurrence of rash, itching, unpleasant odor and the like on the skin surface.

  This silver deposition may be at least part or all of the anodized film of the aluminum material. This antibacterial member is also used so that the antibacterial member is brought into contact with or in close contact with a portion where skin surface irritation is likely to occur.

  In addition, according to the antibacterial member according to claim 3 of the present invention, since the base material is a cloth member, a leather member, or a foamable resin member, the touch is good and uncomfortable feeling is generated even if the skin is directly touched. It can be used without. When the base material is a fabric member, the carbon material or the aluminum material enters the gap between the fibers, and thereby the carbon material or the aluminum material can be mixed in the fabric member. Furthermore, since the cloth member can be cut and processed, an antibacterial member having a shape corresponding to the purpose of use can be produced. When the base material is a leather member, the carbon material or aluminum material enters the gap between the fibers of the leather skin and the concave portion of the skin, thereby mixing the carbon material or aluminum material in the leather member. be able to. Since the leather member can also be cut and processed, an antibacterial member having a shape corresponding to the purpose of use can be produced. Further, when the base material is a foamable resin member, the foamable resin member is porous and has a large number of holes on the surface, and a carbon material or an aluminum material enters into these holes, whereby the foamable resin A carbon material or an aluminum material can be mixed in the manufactured member. Further, since the foamable resin member can be formed into a shape according to the purpose of use by molding, it can be advantageously applied as an antibacterial member to a part where the skin is in contact with or in close contact with.

  Moreover, according to the antibacterial member according to claim 4 of the present invention, silica gel is mixed in at least part of the surface of the base material in addition to the carbon material or the aluminum material. Since silica gel has water absorption, it removes moisture such as sweat and urine that is a nutrient source for the propagation of various bacteria from the skin surface, and can prevent skin irritation, and can suppress the propagation of various bacteria. The feeling of wearing the base material can be improved. Further, since the number of germs is reduced, there is almost no odor due to the breeding, and the generation of odor can be suppressed.

  According to the antibacterial leather material of claim 5 of the present invention, the skin fibers and fibers of the non-conductive leather member are obtained by performing a tanning treatment using a tanning agent containing an aluminum material on the leather member. Aluminum material is mixed in the gap. Since the aluminum material has conductivity, the leather member can be made conductive by mixing the aluminum material with the leather member. Then, by applying a predetermined electrolytic treatment to such a leather member, an anodized film can be provided on at least a part of the surface of the aluminum material mixed in the leather member, and silver is deposited on the anodized film. Can be made. The antibacterial action of silver suppresses the growth of germs and can suppress the occurrence of rash, itching, unpleasant odor, etc. on the skin surface. Moreover, it is possible to prevent bacteria and other germs from propagating on the surface of the leather member due to the antibacterial action of silver. The silver deposition may be at least part or all of the anodized film.

  According to the antibacterial leather material of claim 6 of the present invention, the skin fibers and fibers of the non-conductive leather member are obtained by performing a tanning process using a tanning agent containing a carbon material on the leather member. Carbon material is mixed in the gap. Since the carbon material has conductivity, the leather member can be made conductive by mixing the carbon material with the leather member. And silver can be deposited from the surface of the carbon material mixed in the leather member by performing a predetermined electrolytic treatment on such a leather member. The antibacterial action of silver suppresses the propagation of germs, suppresses the occurrence of rash on the skin surface, and prevents germs and other germs from propagating on the surface of the leather member.

  Moreover, according to the antibacterial leather material of Claim 7 of this invention, in addition to the aluminum material or the carbon material, the silica gel is mixed on the surface of the leather member. Since silica gel has water absorption, it removes moisture such as sweat, which is a nutrient source for the propagation of various bacteria, from the skin surface and prevents skin irritation, and it can suppress the propagation of various bacteria and is made of leather. The feeling of wearing the member can be improved. Further, since the number of germs is reduced, there is almost no odor due to the breeding, and the generation of odor can be suppressed. Furthermore, since silica gel absorbs moisture such as sweat and rain adhering to the leather member, it is possible to prevent bacteria such as mold from growing on the surface of the leather member.

  Moreover, according to the method for producing an antibacterial member according to claim 8 of the present invention, a sulfuric acid bath, an oxalic acid bath or a mixed bath thereof is used as the electrolytic solution, and silver nitrate, silver sulfate, silver nitrate and the like are used in the electrolytic bath. A mixture of silver sulfate is added. Then, since the electrolytic treatment is performed by applying either AC / DC superimposing current, AC current, PR current flowing negative waves or pulse waves flowing negative waves in the electrolyte, carbon mixed in the non-conductive base material Silver can be deposited on the surface of the material. The antibacterial member manufactured in this way can have antibacterial properties due to the precipitated silver, and in a highly humid environment, the precipitated silver is ionized and released to the surroundings, exhibiting a strong antibacterial action. Therefore, it can be used as an antibacterial member that suppresses the propagation of germs and suppresses the generation of odor due to the germs.

  According to the method for producing an antibacterial member according to claim 9 of the present invention, a sulfuric acid bath, an oxalic acid bath, or a mixed bath thereof is used as an electrolytic solution, and silver nitrate, silver sulfate, silver nitrate, and the like are used in the electrolytic bath. A mixture of silver sulfate is added. Then, the electrolytic treatment is performed by applying either an AC / DC superimposed current, an AC current, a PR current that flows a negative wave, or a pulse wave that flows a negative wave in the electrolytic solution. By this electrolytic treatment, an anodized film is formed on the surface of the aluminum material mixed in the non-conductive base material, and at the same time, silver can be deposited on the anodized film. The antibacterial member thus manufactured can have antibacterial properties due to the deposited silver, and can exhibit the same antibacterial action as described above.

Hereinafter, with reference to an accompanying drawing, an antibacterial member according to the present invention, a leather member, and a manufacturing method for them are explained.
First, with reference to FIGS. 1-3, the surface-treated member used as the antibacterial member according to this invention is demonstrated. FIG. 1 is a perspective view schematically showing a cloth member as a base material of an antibacterial member according to the present invention in which a carbon material or an aluminum material is mixed (surface treated member), and FIG. 2 is according to the present invention. FIG. 3 is a perspective view schematically showing a foamed resin member as a base material of an antibacterial member in which a carbon material or an aluminum material is mixed (surface-treated member), and FIG. 3 is a base of the antibacterial member according to the present invention. It is a perspective view which shows simply what mixed the carbon material or the aluminum material in the leather member as a material (surface-treated member).

  In FIG. 1, a cloth member 6 as a base material 4 of an antibacterial member is non-conductive. For example, powdered carbon 8 is mixed in the cloth member 6 as a carbon material, or powdered aluminum 9 is used as an aluminum material. The surface-treated member 10 is formed by mixing them. The powdery carbon 8 or the powdery aluminum 9 is interposed in a state where the powdery carbon 8 or the powdery aluminum 9 enters the gaps between the fibers of the cloth member 6. Can be given.

  In FIG. 2, the foamable resin member 12 as the base material 4A of the antibacterial member is non-conductive, and the foamable resin member 12 is mixed with powdered carbon 8 as a carbon material, or an aluminum material. The surface-treated member 14 is formed by mixing the powdered aluminum 9. The foamable resin member 12 is porous, and the powdered carbon 8 or the powdered aluminum 9 enters the voids in these holes. Thus, the powdered carbon 8 or the powdered aluminum 9 is mixed. Thus, the foamable resin member 12 can be made conductive.

  In FIG. 3, the leather member 16 as the base material 4B of the antibacterial member is non-conductive, and the powdery carbon 8 as the carbon material is mixed in the leather member 16 or the powdery material as the aluminum material. Surface treated member 18 is formed by mixing aluminum 9. The powdered carbon 8 or the powdered aluminum 9 is interposed in a state where it enters the protein collagen of the skin of the leather member 16, and the powdered carbon 8 or the powdered aluminum 9 is mixed in this way, so that the leather member 16 is mixed. Conductivity can be imparted.

  The cloth of the cloth member 6 is a nonwoven fabric or a woven cloth, and the foamable resin of the foamable resin member 12 is a polyurethane resin, a polypropylene resin, a polyethylene resin, a polystyrene resin, or the like. The shape of the cloth member 6 may be a fabric shape before cutting, and the shape of the foamable resin member 12 may be various shapes depending on the purpose of use. For example, a thin plate shape, a film shape, a block shape, It is formed into a container shape or the like. The leather of the leather member 16 is leather such as cow or pig, and the shape thereof is formed into a sheet shape.

  As a method of mixing the powdery carbon 8 in these base materials 4, 4A, 4B (cloth member 6, foamable resin member 12, leather member 16), the cloth member 6, foamable resin member 12 or leather is used. An inorganic material in which powdery carbon 8 is mixed by mixing powdery carbon 8 directly into, for example, an inorganic adhesive 20 as an adhesive at a predetermined portion of the surface of the member 16 (that is, a portion where powdered carbon 8 is desired to be mixed). It applies by applying so that the system adhesive 20 may be applied. In the case of the cloth member 6, the inorganic adhesive 20 enters the gap between the fibers of the cloth member 6 and is mixed so that the powdered carbon 8 adheres around the fibers. Further, in the case of the foamable resin member 12, the inorganic adhesive 20 enters the voids in the pores of the foamable resin member 12, and the powdered carbon 8 is mixed in the adhesive 20 in the voids. Further, in the case of the leather member 16, the inorganic adhesive 20 enters the gap between the fibers of the leather skin and the concave portion of the skin, and the powdery carbon 8 is mixed in the adhesive 20 in the gap or the concave portion. The Thus, the powdery carbon 8 can be mixed in a desired portion of the surface of the cloth member 6, the foamable resin member 12, or the leather member 16. Since the inorganic adhesive 20 is less harmful to the skin and the like, it can be advantageously applied to the cloth member 6, the foamable resin member 12, or the leather member 16 that directly contacts or adheres to the skin or the like. In addition, the inorganic adhesive has little decrease in adhesive force when performing an electrolytic treatment for precipitating silver on the powdery carbon 8 described later.

  As another method of mixing the powdery carbon 8 in the base materials 4, 4 </ b> A, 4 </ b> B, an inorganic adhesive 20 is applied to a desired portion of the cloth member 6, the foamable resin member 12, or the leather member 16. Then, it may be applied by spraying powdered carbon 8 on the inorganic adhesive 20 and then pushing it into the adhesive 20. In this case as well, the cloth member 6 is the same as described above. The powdery carbon 8 can be mixed on the surface of the foamable resin member 12 or the leather member 16.

  If a large amount of powdered carbon 8 is used, the powdered carbon 8 is a gap between the fibers of the fabric member 6, a gap in the hole of the foamable resin member 12, or a gap between the fibers of the leather member 16 or the skin. May not be able to enter the concave portion of the material, and may be exposed on the surfaces of the cloth member 6, the foamable resin member 12, and the leather member 16, and the touch and the like may be deteriorated. For this reason, it is desirable that the powdered carbon 8 is in the form of fine powder.

  Furthermore, as another method of mixing the powdered carbon 8 in the foamable resin member 12 as the base material 4A, the powdered carbon 8 is mixed in the resin before molding, and the powdered carbon 8 is mixed. In this way, the resin may be molded. By doing so, the powdery carbon 8 can be mixed uniformly in the entire foamable resin member 12.

  Next, as a method of mixing the powdered aluminum 9 in the base materials 4, 4 </ b> A, 4 </ b> B, the method of mixing the powdered carbon 8 is performed by using the powdered aluminum 9 instead of the powdered carbon 8. be able to. That is, powdery aluminum 9 is directly mixed in the inorganic adhesive 20, and the inorganic adhesive 20 mixed with the powdered aluminum 9 is used as a desired part of the cloth member 6, the foamable resin member 12, or the leather member 16. Powdered aluminum 9 can be mixed so as to be applied to the surface. In addition, the inorganic adhesive 20 is applied to a desired portion of the cloth member 6, the foamable resin member 12, or the leather member 16, and then powdered aluminum 9 is applied to the inorganic adhesive 20. Even if it pushes in, the powdered aluminum 9 can be mixed. Further, in the case of the foamable resin member 12, the powdered aluminum 9 may be mixed into the resin before being molded, and the resin may be molded in a state where the powdered aluminum 9 is mixed.

  In the above-described method of mixing the aluminum material with the base materials 4, 4 </ b> A, 4 </ b> B, powdered aluminum 9 is used instead of powdered carbon 8, but powdered aluminum 9 is used together with powdered carbon 8. Thus, the powdery carbon 8 and the powdered aluminum 9 can be mixed in the base materials 4, 4 </ b> A, 4 </ b> B.

  Next, a method of mixing an aluminum material with a tanning agent in the leather member 17 as the base material 4C of the antibacterial member will be described with reference to FIG. FIG. 4 is a perspective view schematically showing a leather member as an antibacterial member according to the present invention in which an aluminum material is mixed with a tanning agent (surface-treated member). In FIG. 4, the surface-treated member 19 is formed by mixing, for example, powdered aluminum 9 as an aluminum material with the leather member 17. The powdered aluminum 9 is subjected to a tanning process using a tanning agent containing the powdered aluminum 9 on the leather member 17, whereby the powdered aluminum 9 can be mixed and the leather member 17 can be made conductive. The tanning process is one of the leather making processes in which a leather is subjected to a chemical process on protein collagen in raw hides such as cows and pigs, thereby giving the leather flexibility and breathability. By applying a tanning treatment to the leather member 17 using a tanning agent containing powdered aluminum 9 as the tanning agent, the powdered aluminum 9 enters the protein collagen of the leather skin of the leather member 17, and the leather member 17. Powdered aluminum 9 can be mixed.

  In addition, as a method of mixing the carbon material in the leather member 17, it can be performed by using a carbon material instead of the powdered aluminum 9 in the tanning process described above. That is, as a carbon material, for example, by applying a tanning treatment to the leather member 17 using a tanning agent containing powdered carbon 8, the powdery carbon 8 enters the protein collagen of the leather skin of the leather member 17, As a result, the powdery carbon 8 can be mixed in the leather member 17.

  It is also possible to mix the powdered aluminum 9 and the powdered carbon 8 in the leather member 17 by mixing the powdered aluminum 8 together with the powdered aluminum 9 in the tanning agent and subjecting the leather member 17 to the tanning treatment. .

  Next, a surface treatment using the surface-treated member 10 (14, 18, 19) formed as described above, that is, a method for manufacturing the antibacterial member 2 will be described with reference to FIG. FIG. 5 is a simplified diagram schematically showing an example of a surface treatment apparatus used for carrying out the manufacturing method according to the present invention.

  In FIG. 5, the illustrated surface treatment apparatus includes a rectangular parallelepiped electrolytic cell 22, and electrodes 24 and 26 are disposed on both sides of the electrolytic cell 22. In this embodiment, the electrodes 24 and 26 are composed of four plate-like electrodes 28 and 30 arranged at intervals in the longitudinal direction of the electrolytic cell 22 and in the left-right direction in FIG. 30 is formed of carbon. The electrodes 24 and 26 are electrically arranged in parallel, the four plate electrodes 28 of one electrode 24 are electrically connected in series, and the four plate electrodes 30 of the other electrode 26 are electrically connected. Connected in series.

  Surface treated members 10, 10 (14, 14) (18, 18) (19, 19) to be surface treated between the pair of electrodes 24, 26 (hereinafter referred to as “surface treated members 10, 10 etc.”) Is disposed. One surface-treated member 10 (14, 18, 19) (hereinafter referred to as “surface-treated member 10 etc.”) is disposed inside and opposed to the electrode 24, and the other surface-treated member 10 etc. Opposite the electrode 26 is disposed inside. This surface treatment apparatus performs surface treatment on the surface treated members 10, 10 formed from the cloth member 6, the foamable resin member 12, or the leather members 16, 17 as described later.

  The electrolytic bath 22 is filled with an electrolytic solution for surface treatment, and the surface-treated members 10 and 10 to be treated are immersed in the electrolytic solution. As the electrolytic solution, a sulfuric acid bath, an oxalic acid bath, or a mixed bath thereof is used. Then, silver nitrate as a metal nitrate, silver sulfate as a metal sulfate, or a mixture of silver nitrate and silver sulfate is added to such an electrolytic bath. When using a sulfuric acid bath, sulfuric acid is dissolved at a rate of, for example, 100 to 300 g / liter, and when using an oxalic acid bath, oxalic acid is dissolved at a rate of, for example, 20 to 40 g / liter.

  Further, silver nitrate or silver sulfate added to such an electrolytic bath is added at a rate of 2 g / liter or more, for example. When the amount of silver nitrate or silver sulfate is less than 2 g / liter, the amount of silver deposited when the surface treatment is performed decreases.

  When surface treatment is performed on the surface-treated members 10, 10, etc., an AC / DC superimposed current, that is, a current in which an alternating current and a positive current of a direct current are superimposed is applied to the surface-treated members 10, 10, etc. Electrolytic treatment is performed on the surface-treated members 10 and 10 by applying such current. In this embodiment, the plus side of the DC power supply 32 is electrically connected to the reactor 34, and the minus side of the DC power supply 34 is electrically connected to the electrodes 24 and 26 (plate-like electrodes 28 and 30). Further, the AC power source 36 is electrically connected to the reactor 34, and the reactor 34 superimposes the positive current of the DC power source 32 on the AC current from the AC power source 36, and the surface-treated member that should process the superimposed superimposed current. It will be sent to 10, 10 etc.

During the surface treatment, the current density is selected to be in the range of, for example, 1 to 10 A / dm ^{2 and} the current density is continuously energized for a predetermined set time. When the current density exceeds 10 A / dm ² , damage due to discharge is likely to occur at the contact portion between the surface treated members 10, 10 and the like and the jig holding the member. On the other hand, when the current density is smaller than 1 A / dm ² , the current flowing in the electrolyte is small, and the surface treatment efficiency is deteriorated.

  At the time of this surface treatment, the temperature of the electrolytic bath is selected to be in the range of, for example, −10 to 25 ° C. When the temperature of the electrolytic bath exceeds 25 ° C., it becomes difficult to deposit silver uniformly on the surface of the powdery carbon 8 mixed in the surface-treated members 10, 10 and the like. On the other hand, when the temperature of the electrolytic bath is lower than −10 ° C., the treatment efficiency of the surface treatment is deteriorated and the surface treatment cost is increased.

  When surface treatment is performed on the surface-treated member 10 or the like with the surface treatment apparatus described above, silver is deposited on the surface of the powdered carbon 8 mixed in the surface-treated member 10 or the like. Further, in the powdered aluminum 9 mixed in the surface-treated member 10 or the like, an anodized film is formed on the surface of the powdered aluminum 9, and the anodized film is formed simultaneously with the formation of the anodized film. Silver nitrate (or silver sulfate) silver is deposited in a large number of pores existing in the porous layer. Thus, antibacterial property is imparted by the silver deposited on the surface-treated member 10 or the like. When the surface-treated member 10 is the cloth member 6, the produced antibacterial member 2 is as shown in FIG. 6, and when the surface-treated member 14 is the foamable resin member 12, the produced antibacterial member 2A. 7 is as shown in FIG. 7, and when the surface-treated member 19 is a leather member 17, the produced antibacterial member 2B is as shown in FIG. FIG. 6 is an enlarged cross-sectional view schematically showing a state in which silver is deposited on the surface of powdered carbon (powdered aluminum) mixed in the cloth member, and FIG. 7 is mixed in the foamable resin member. FIG. 8 is an enlarged cross-sectional view schematically showing a state in which silver is deposited on the surface of powdered carbon (powdered aluminum). FIG. 8 is a diagram of powdered carbon (powdered aluminum) mixed in a leather member by tanning. It is an expanded sectional view which shows simply the state which silver was deposited on the surface of).

  In FIG. 6, when the base material 4 is a cloth member 6, an adhesive 20 in which powdery carbon 8 (powdered aluminum 9) is mixed is applied to a gap between the fibers 39 of the cloth member 6. The powdery carbon 8 (powdered aluminum 9) is mixed so as to adhere to the surface, and the surface of the mixed powdery carbon 8 (an anodized film formed on the powdery aluminum 9) (contacts the electrolyte). Silver 38 of silver nitrate (or silver sulfate) is deposited on the surface).

  In FIG. 7, when the base material 4 </ b> A is the foamable resin member 12, the adhesive 20 in which powdered carbon 8 (powdered aluminum 9) is mixed in the hole 41 on the surface of the foamable resin member 12 is applied. Rarely, silver 38 of silver nitrate (or silver sulfate) is deposited on the surface of the mixed powdery carbon 8 (an anodic oxide coating formed on the powdered aluminum 9) (the surface in contact with the electrolyte).

  In FIG. 8, when the base material 4C is the leather member 17, the powdered carbon together with the tanning agent 44 is formed in the gaps between the protein collagen fibers 42 on the skin of the leather member 17 and the concave portions 46 on the surface of the fibers 42 by the tanning process. 8 enters and the powdery carbon 8 is mixed in the gaps between the protein collagen fibers 42 and the concave portions 46, and silver nitrate (or silver sulfate) is present on the surface of the mixed powdery carbon 8 (surface in contact with the electrolyte). Of silver 38 is deposited.

  When the leather member 17 is tanned with a tanning agent containing powdered aluminum 9, the powdered aluminum 9 enters the gaps between the protein collagen fibers 42 and the concave portions 46, and the powdered aluminum 9 is mixed. The surface of the mixed powdery aluminum 9 (the surface in contact with the electrolytic solution) is anodized by a barrier layer and a porous layer formed on the surface of the barrier layer by the surface treatment described above. A film is formed, and silver nitrate (or silver sulfate) silver 38 is deposited in a large number of pores existing in the porous layer.

  The silver 38 deposited on the base material 4 (4A, 4B, 4C) has an antibacterial action, and by this antibacterial action, the surface treated members 10, 14, 18, 19 are convenient as the antibacterial members 2, 2A, 2B, 2C. By using these antibacterial members 2, 2A, 2B, and 2C, it is possible to suppress propagation of germs and keep them clean. In particular, the silver 38 deposited by the above-described processing method is ionized and released to the surroundings in a watery environment (for example, when immersed in water or placed in a humid environment), and the ionized silver is strong. It exerts antibacterial action and can obtain strong antibacterial action.

  In the above-described embodiment, the electrolytic treatment is performed by applying the AC / DC superimposed current when the surface treatment is performed. However, instead of the AC / DC superimposed current, an AC current, a PR current for passing a minus wave, or a pulse for passing a minus wave is added. However, as described above, a predetermined surface treatment can be performed, and silver 38 can be deposited on the surface of the surface-treated member 10 or the like. For example, a surface treatment apparatus that performs surface treatment by applying an alternating current includes a rectangular parallelepiped electrolytic bath, and a pair of electrodes similar to those described above are disposed on both sides of the electrolytic bath. A surface-treated member is disposed between the two. The electrolytic layer is filled with the same electrolytic solution as in the case of performing the electrolytic treatment by applying the AC / DC superimposed current, and an AC power source is connected to the pair of electrodes and the surface-treated member, An alternating current is passed through the surface treatment member at the temperature of the electrolytic bath, and the surface treatment member is subjected to a predetermined surface treatment.

  In the embodiment described above, an anodic oxide film is formed on the surface of the powdered aluminum 9 mixed in the base material 4 (4A, 4B, 4C) by a single electrolytic treatment, and at the same time, silver is added to the anodic oxide film. However, the formation of the anodized film and the deposition of silver 38 may be performed in separate steps. In this case, the base material 4 (4A, 4B, 4C) is immersed in a sulfuric acid bath, an oxalic acid bath, or a mixed bath thereof, anodized, and then subjected to electrolytic treatment with an electrolytic solution to which silver nitrate or silver sulfate is added. Even if it does in this way, formation of an anodic oxide film and precipitation of silver on this anodic oxide film can be similarly performed. In this case, as the current of the electrolytic treatment, a predetermined electrolytic treatment is performed by adding various currents such as an AC / DC superimposed current, an alternating current, a PR current passing a negative wave, or a pulse current passing a negative wave. It can be carried out.

  In the above-described embodiment, the powdery carbon 8 or the powdery aluminum 9 is mixed in the base material 4 (4A, 4B, 4C). The silica gel may be mixed. The method of mixing powdery silica gel in the base material 4 (4A, 4B, 4C) can be performed by the same method as the method of mixing powdered carbon 8 or powdered aluminum 9. That is, in the base material 4 (4A, 4B), the inorganic adhesive 20 mixed with the powdered carbon 8 and the powdered silica gel is applied so as to be applied, and the gap between the fibers 39 of the cloth member 6 or The adhesive 20 mixed with the powdered carbon 8 and the powdered silica gel can be applied into the numerous holes 41 on the surface of the foamable resin member 12 so that the powdered silica gel is mixed. The foamable resin member 12 may be molded by mixing the powdery carbon 8 and the powdered silica gel in the foamable resin before molding. Further, in the base material 4C, the powdery silica gel is mixed in the tanning agent, and the leather member 17 is tanned using this tanning agent, so that the leather is similar to the powdered carbon 8 or the powdered aluminum 9. Powdered silica gel can be mixed in the member 17.

  In the antibacterial member 2 (2A, 2B, 2C) in which the base material 4 (4A, 4B, 4C) is mixed with powdered silica gel, in addition to the sterilizing action of the silver 38 deposited on the powdered carbon 8 or the powdered aluminum 9 Thus, the water absorption action and deodorization action of silica gel mixed in the base material 4 (4A, 4B, 4C) can be obtained, the odor can be adsorbed, and moisture such as sweat and urine can be absorbed. In addition to preventing skin irritation, it is possible to remove moisture to further suppress the growth of germs and to further suppress the generation of odors.

  The antibacterial member 2 (2A, 2B, 2C) manufactured by the surface treatment described above can be used for various products for suppressing the propagation of various bacteria, the generation of odor, skin irritation, and the like. When the base material is the fabric member 6, it can be cut, so it can be processed into various fabric products according to the purpose of use. For example, when used as a bed or a sheet of a futon, Bed slippage can be prevented, and when used in a filter such as a curtain or a deodorizing device, an unpleasant odor in the room can be adsorbed by the odor adsorbing action. In addition, when used for clothes, underwear, diapers, insoles of shoes, interior members for casts, etc., it is possible to suppress the occurrence of skin irritation, itching, etc. due to secretions such as sweat and fat.

  Further, when the base material is the foamable resin member 12, since the foamable resin is a polyurethane resin, a polypropylene resin, a polyethylene resin, or a polystyrene resin, an antibacterial action can be given to a member that is touched in daily life. it can. For example, polyurethane resin is used in armrests of chairs, polypropylene resin is used in washbasins, polyethylene resin is used in packaging films, polystyrene resin is used in packaging materials for food containers, etc. It can have an effect.

  Further, when the base material is a leather member 16, 17, it can be cut, so it can be processed into various leather products according to the purpose of use. For example, when used for leather shoes or leather pants. The generation of unpleasant odor due to secretions such as sweat can be suppressed. In addition, the antibacterial action of silver can suppress the proliferation of germs and other germs on the leather product itself.

[Examples and Comparative Examples]
Example 1
In order to confirm the antibacterial effect of the deposited silver, a surface treatment was performed on the base material of the nonwoven fabric under the following conditions.
As Example 1, the surface treatment apparatus shown in FIG. 5 was used, and an electrolytic treatment was performed using an electrolytic solution obtained by adding 5 g / liter of silver sulfate to a sulfuric acid bath of 100 g / liter of sulfuric acid. A non-woven fabric (length 50 mm x width 50 mm x thickness 0.5 mm) is used as a base material. After coating the non-woven fabric with an inorganic adhesive, it is sprayed so as to embed powdery carbon in the inorganic adhesive. The powdered carbon was mixed in the non-woven fabric so as to be pushed into. The nonwoven fabric was subjected to electrolytic treatment with the anode (plus) side and the carbon electrode with the cathode (minus) side. The temperature of the electrolytic solution during the electrolytic treatment was 15 ° C., and during the electrolytic treatment, an AC / DC superimposed current with an AC / DC current ratio of 1: 1 was applied. The current density of this electrolytic current was 1.0 A / dm ² , and the electrolytic treatment was performed for 10 minutes under the above conditions, and silver was deposited on the powdery carbon mixed in the nonwoven fabric.

Example 2
As Example 2, the same surface treatment apparatus as in Example 1 was used, and a woven fabric (length 50 mm × width 50 mm × thickness 0.5 mm) was used as a base material. The woven fabric mixed with powdered carbon was subjected to electrolytic treatment using an electrolytic solution obtained by adding 10 g / liter of silver nitrate to a sulfuric acid bath of 200 g / liter of sulfuric acid. The conditions for the electrolytic treatment were the same as those in Example 1. Silver was deposited on the powdered carbon mixed in the woven fabric after the electrolytic treatment.

Comparative Example As a comparative example, a non-woven fabric as a base material was used without surface treatment.
Suppression confirmation test such as itch and rash of leg and finger fracture part Examples 1 and 2 and comparative example, when wearing casts on leg and finger fracture part, such as itch and rash on wearing part A suppression confirmation test was conducted. In the fractured part of the leg, each of the six patients was attached with the Examples 1 and 2 and the comparative example wrapped around the site to be treated before the Gibbs was worn, and the Gibbs was worn. And the occurrence of itching of the skin with the passage of time after the attachment was examined. Also, in the finger fracture part, each of two other six patients is packed with aluminum fixing brackets in Examples 1 and 2 and the comparative example, and the packaged fixing brackets are attached to the fracture portions. The surrounding area was wrapped with a wrapping bag to fix the finger, and the occurrence of itching of the skin over time after the attachment was examined. The results of this confirmation test were as shown in Table 1.

表１の結果から理解されるように、脚の骨折部において、実施例１及び２を用いた抗菌部材では、いずれもギブスを装着していた２１日間、２人の患者のいずれにおいても脚の骨折部の皮膚の痒みは発生しなかった。また２１日目にギブスを外して皮膚の状態を確認したところ、実施例１及び２ともにかぶれは発生しておらず、またギブスの内側部に不快な臭いも発生していなかった。

As can be understood from the results in Table 1, the antibacterial member using Examples 1 and 2 at the fractured part of the leg had 21 days in both patients for 21 days when both casts were worn. No itching of the fractured skin occurred. On the 21st day, the cast was removed and the skin condition was confirmed. In both Examples 1 and 2, no rash occurred, and no unpleasant odor occurred on the inner side of the cast.

  In contrast, in the comparative example, itching occurred from the third day in both of the two patients, and itching became severe on the seventh day. On day 21, the cast was removed and the condition of the skin was confirmed. The rash was also severe, and a bad odor was generated inside the cast.

  In addition, in the finger fracture part, the antibacterial members using Examples 1 and 2 both had the skin of the finger fracture part in both of the two patients for 7 days while wearing the fixing bracket and the wrapping bag. There was no itch. Moreover, when the cast was removed on the 7th day and the condition of the skin was confirmed, rash did not occur in both Examples 1 and 2, and no unpleasant odor occurred in the inner part of the fixture.

  In contrast, in the comparative example, itching occurred from the third day in both of the two patients, and itching became severe on the seventh day. On the seventh day, the fixing bracket and the sachet were removed, and the skin condition was confirmed. As a result, rash occurred, and a little odor was generated inside the fixing bracket.

Thus, those using Examples 1 and 2 did not cause itchiness or rash at the fractured part of the legs and fingers, and the antibacterial action according to the present invention could be confirmed.
[Silver ion deposition confirmation test]
Under the conditions of Example 1, an adhesive mixed with powdered carbon was applied to the entire surface of one nonwoven fabric, powdered carbon was mixed in the nonwoven fabric, electrolytic treatment was performed using this nonwoven fabric, and mixed in this nonwoven fabric. It was confirmed whether or not silver ions were deposited on the powdered carbon. For the measurement, a silver ion meter manufactured by Hanna Instruments Inc. (Italy) was used. Specifically, first, one end of this nonwoven fabric (the end far from the end connected to the power source) was cut into a size of 5 cm × 5 cm and immersed in 500 ml of water for 10 minutes. Thereafter, 50 ml was extracted from this water, a dedicated reagent was added to this 50 ml of water, silver ions were emitted by the reaction of this dedicated reagent and silver ions in water, and the concentration of silver ions was measured by absorptiometry. . The measurement was carried out by measuring the silver ion concentration after 32 minutes with reference to the time when the dedicated reagent was added. As a result, the measured silver ion concentration was 0.023 ppm, and it was confirmed that the nonwoven fabric using Example 1 precipitated silver ions.

It is a perspective view which shows simply what mixed the carbon material or the aluminum material with the cloth member as a base material of the antibacterial member according to this invention. It is a perspective view which shows simply what mixed the carbon material or the aluminum material with the foaming resin member as a base material of the antibacterial member according to this invention. It is a perspective view which shows simply what mixed the carbon material or the aluminum material with the leather member as a base material of the antibacterial member according to this invention. It is a perspective view which shows simply what mixed the aluminum material with the tanning agent in the leather member as an antibacterial member according to the present invention. It is a simplified diagram which shows simply an example of the surface treatment apparatus used in order to carry out the manufacturing method according to the present invention. It is an expanded sectional view showing simply the state where silver was deposited on powdery carbon or powdery aluminum mixed in a cloth member as a base material. It is an expanded sectional view showing simply the state where silver was deposited on powdery carbon or powdery aluminum mixed in a foamable resin member as a base material. It is an expanded sectional view showing simply the state where silver was deposited on the surface of powdery carbon or powdery aluminum mixed in a leather member by tanning.

Explanation of symbols

2, 2A, 2B, 2C Antibacterial member 4, 4A, 4B, 4C Base material 6 Fabric member 8 Powdered carbon 10, 14, 18, 19 Surface treated member 12 Expandable resin member 16, 17 Leather member 20 Inorganic Adhesive 22 Electrolytic cell 24, 26 Electrode 32 DC power supply 36 AC power supply 38 Silver

Claims (9)

  An antibacterial member characterized in that a carbon material is mixed in at least a part of the surface of a non-conductive base material, and silver is deposited on the surface of the carbon material.   An antibacterial member characterized in that an aluminum material is mixed in at least a part of the surface of a non-conductive base material, and silver is deposited on an anodized film formed on the surface of the aluminum material.   The antibacterial member according to claim 1 or 2, wherein the base material is a cloth member, a leather member, or a foamable resin member.   The antibacterial member according to any one of claims 1 to 3, wherein silica gel is further mixed in at least a part of the surface of the base material.   Antibacterial characterized in that aluminum material is mixed by tanning treatment using a tanning agent containing aluminum material on the surface of the leather member, and silver is deposited on the anodized film formed on the surface of the aluminum material. Leather material.   An antibacterial leather material characterized in that a carbon material is mixed by performing a tanning treatment using a tanning agent containing a carbon material on a surface of a leather member, and silver is deposited on the surface of the carbon material.   The antibacterial leather material according to claim 5 or 6, wherein silica gel is further mixed on a surface of the leather member.   A non-conductive base material mixed with a carbon material is subjected to an AC / DC superimposed current in an electrolytic solution in which silver nitrate or silver sulfate or a mixture of silver nitrate and silver sulfate is added to a sulfuric acid bath or an oxalic acid bath or a mixed bath thereof. Electrolytic treatment was carried out by adding either an alternating current, a PR current flowing a negative wave, or a pulse wave flowing a negative wave, thereby precipitating the added silver nitrate or silver sulfate silver on the surface of the carbon material. A method for producing an antibacterial member.   A non-conductive base material mixed with an aluminum material is subjected to an AC / DC superimposed current in an electrolytic solution in which silver nitrate or silver sulfate or a mixture of silver nitrate and silver sulfate is added to a sulfuric acid bath or an oxalic acid bath or a mixed bath thereof. Then, either an alternating current, a PR current that flows a negative wave, or a pulse wave that flows a negative wave is subjected to electrolytic treatment, thereby forming an anodic oxide film on the surface of the aluminum material, and simultaneously adding silver nitrate or silver sulfate. A method for producing an antibacterial member, characterized by depositing silver on the anodized film.

Images