JPH0860341A - Surface treatment of ornament having antibacterial property - Google Patents

Abstract

PURPOSE: To provide a method for surface-treating an ornament having an antibacterial property capable of maintaining a high antibacterial property over a long period. CONSTITUTION: A composite plating layer 8, wherein a powdery antibacterial agent 7 is uniformly distributed, is formed on a substrate 1 by ion plating or sputtering from the mixed powder of the antibacterial agent 7 obtained by replacing a part of calcium phosphate as an inorg. carrier silver as an antibacterial metal ion and Ti as a plating metal. Meanwhile, at least one kind selected from a group consisting of copper, zinc, tin, bismuth and chromium is used as the antibacterial metal ion besides silver. Further, a material consisting essentially of rutile-type titanium oxide is used as the powdery antibacterial agent. Consequently, an ornament, on which the composite plating layer 8 is formed, maintains a high antibacterial property over a long period, and the color tone and luster inherent in plating are not adversely affected.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment method for ornaments such as eyeglass frames, watches, lighters, fountain pens and broaches having a composite plating layer formed on the surface thereof, and in particular, the composite plating layer has antibacterial properties. Related to what is configured. By the way, in the present specification, the term antibacterial property means that bacteria and / or
It also means the property of suppressing the reproduction of mold.

[0002]

2. Description of the Related Art The surface treatment method of this kind of ornaments that has been performed conventionally is by spray coating or electrodeposition coating with a paint mixed with an antibacterial agent on the plated surface of ornaments such as eyeglass frames. It was to apply.

[0003]

However, in the above-mentioned prior art example, the antibacterial agent is mixed into the paint to reduce the adhesion of the paint to eyeglass frames and the like, and the paint originally has ultraviolet rays, sweat and abrasion. However, since it is extremely vulnerable to alcohol and the like, there is a problem that the antibacterial effect disappears by peeling off about 3 months after the start of use.

Further, in terms of commercial value, the color tone of the plated products of each of the above-mentioned ornaments is emphasized. However, since the paint and the antibacterial agent are not completely transparent, ultraviolet rays, If it is formed thick to prevent peeling and damage due to sweat, abrasion, alcohol, etc., the surface of plated decorative products will be covered with the paint and antibacterial agent, so the original color tone of the plating will change and the commercial value will decrease. There was a problem to do. In particular, in the case of a decorative article which is plated with a noble metal, this problem becomes remarkable.

Further, since the antibacterial agent has a larger specific gravity than the paint, it is difficult to uniformly disperse the antibacterial agent in the paint, and the distribution of the antibacterial agent or the like in each part of the decorative article varies.
There was a problem that many things became defective.

The present invention has been made to solve the above-mentioned problems, and has been made to solve the problems. A method for surface treatment of a decorative article having a strong antibacterial property against ultraviolet rays, sweat, abrasion, alcohol, etc. The purpose is to provide.

It is another object of the present invention to provide a surface treatment method for a decorative article which has a high antibacterial property for a long period of time and has an antibacterial property which does not adversely affect the original color tone and luster of plating. .

[0008]

In order to achieve the above objects, the present invention provides a powdered antibacterial agent 7 obtained by substituting a part of an inorganic carrier with antibacterial metal ions, and a plating metal. A composite plating layer in which the powdered antibacterial agent 7 is evenly distributed on the substrate 1 by an ion plating method or a sputtering method in which a mixture of the above is heated and reacted with a predetermined reaction gas. 8 is formed.

In order to achieve the above objects, the present invention uses a plating solution in which a powdered antibacterial agent obtained by substituting a part of an inorganic carrier with antibacterial metal ions is uniformly mixed. By the wet plating method, the powdered antibacterial agent and the metal in the plating solution are co-deposited on the substrate to form a composite plating layer in which the powdered antibacterial agent 7 is uniformly distributed.

Calcium phosphate is used as the inorganic carrier, and the antibacterial metal ion is at least one selected from the group consisting of silver, copper, zinc, tin, bismuth and chromium. It is preferable from the viewpoint of obtaining a powdery antibacterial agent having high antibacterial properties.

Further, in order to achieve the above objects, the present invention requires heating, for example, by uniformly mixing a powdered antibacterial agent containing rutile titanium oxide as a main component and a plating metal. A composite plating layer in which the powdered antibacterial agent is uniformly distributed is formed on the base material by an ion plating method or a sputtering method which is performed by reacting with a predetermined reaction gas according to the above.

Further, in order to achieve each of the above objects, the present invention provides, for example, by a wet plating method using a plating solution in which a powdered antibacterial agent containing rutile titanium oxide as a main component is uniformly mixed, The powdered antibacterial agent and the metal in the plating solution are co-deposited on the base material to form a composite plating layer in which the powdered antibacterial agent 7 is uniformly distributed.

The powdered antibacterial agent preferably has a particle size of 1 μm or less from the viewpoint of further preventing deterioration in gloss. When particularly excellent gloss is required, it is desirable that the particle size be 0.1 μm or less. Further, each of the powdered antibacterial agents has a viewpoint of maintaining the antibacterial property for a longer period of time by maintaining a stable adhesive force and not easily peeling, regardless of the environment in which the ornament is used. From the viewpoint of more surely preventing the adverse effect of the above, it is preferable that the composite plating layer contains 0.05 to 20% by weight.

[0014]

As described above, the decorative article in which the composite plating layer 8 in which the powdered antibacterial agent 7 is uniformly distributed by plating is formed on the base material 1 as described above is mixed with the antibacterial agent over the plated surface. Powdered antibacterial agent 7
Exists in and on the surface of the composite plating layer 8 and has strong adhesiveness and is difficult to be peeled off. Therefore, high antibacterial property can be maintained for a long period of time, and further the original color tone and luster of plating can be maintained. In addition, when the powdered antibacterial agent 7 is contained in the composite plating layer 8 in an amount of 0.05% to 20% by weight, the above decorative article has a more stable antibacterial property regardless of the use environment. And the change of the color tone due to the mixing of the powdered antibacterial agent 7 does not occur. Furthermore, when the particle size of the powdered antibacterial agent 7 is 1 μm or less, it is possible to more reliably prevent a decrease in gloss due to the mixing of the powdered antibacterial agent 7.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred first embodiment of the present invention applied to an ion plating method for eyeglass frames will be described in detail below with reference to the accompanying drawings. Here, FIG. 1 is a front view of the spectacle frame, FIG. 2 is an enlarged partial vertical cross-sectional view of the spectacle frame, and FIG. 3 is a schematic vertical cross-sectional view of the ion plating apparatus.

As shown in FIG. 1, first, a Ti wire rod is formed into a shape of an eyeglass frame A1 to obtain a base material 1.

Next, as shown in FIG. 3, the substrate 1 is set in an ion plating device. In this ion plating apparatus, an upper cathode electrode 3 and a lower evaporation source board 4 are arranged in a vacuum processing tank 2 so as to face each other, and the substrate 1 is detachably suspended on the cathode electrode 3. It is structured so that it can be carried. The evaporation source board 4 is provided with a heater 6 connected to the anode of a variable DC power source 5, so that the evaporation source board 4 can be controlled to a desired temperature by adjusting the output of the DC power source 5. Is configured. The cathode of the DC power supply 5 is connected to the cathode electrode 3.

Subsequently, 90% by weight of Ti powder, which is a metal for plating, and 10% by weight of a powdery antibacterial agent 7 having a particle size of 0.3 μm are uniformly mixed with the evaporation source board 4 and obtained. The mixed powder is placed, and the evaporation source board 4 is heated to a desired temperature while flowing nitrogen and acetylene gas as reaction gases into the vacuum processing tank 2. The base material 1 has a particle size of 0.
About 0.5μ containing about 1% by weight of powdered antibacterial agent 7 of 3μm
An m-thick composite plating layer 8 is formed to obtain a spectacle frame A1 as an ornament. The powdered antibacterial agent 7 is obtained by substituting a part of calcium phosphate as an inorganic carrier with silver as an antibacterial metal ion.

As shown in FIG. 2, when observed under a microscope, the powdered antibacterial agent 7 is substantially evenly distributed in the composite plating layer 8 and is almost exposed in the outer surface of the composite plating layer 8. They are evenly distributed, and due to this uniform distribution, they exhibit antibacterial properties without variation.

Subsequently, the spectacle frame A1 and the base material 1
A spectacle frame B1 (conventional example, not shown), which has been plated with Ti powder by an ion plating method and then electrodeposition-coated with a paint containing a powdered antibacterial agent 7,
A spectacle frame C1 obtained by plating the base material 1 by an ion plating method using Ti powder without using an antibacterial agent.
A Cass test was performed to compare the sterilization rate (not shown) and changes in the sterilization rate with time. The results are shown in Table 1.

[Table 1]

From these results, both the spectacle frame A1 and the spectacle frame B1 had a sterilization rate of 9 before the Cass test.
Although it is 9.9%, after 24 hours of the test, the spectacle frame A1 is 99.9%, which is the same as before the test, whereas the spectacle frame B1 is decreased to 52.0%. That is, it was found that the spectacle frame A1 maintains a high sterilization rate (a measure of presence or absence of antibacterial property) for a long period of time as compared with the spectacle frame B1. Further, when observing the color tone and gloss with the naked eye, the spectacle frame A1 shows that the spectacle frame C
It was confirmed that the spectacle frame B1 was inferior to the quantitative frames A1 and C1 on the other hand, while being comparable with No. 1.

The second preferred embodiment of the present invention applied to the eyeglass frame sputtering method will be described in detail below.

First, a 3.0 μm-thick palladium-plated (corrosion-resistant) nickel-white wire is molded into a spectacle frame shape to form a base material (not shown, see FIG. 1).

Next, the above-mentioned base material, 90% by weight of Ti powder as a metal for plating, and the powdery antibacterial agent 7 of the first embodiment were placed in a commonly used general sputtering apparatus (not shown). A sputtering target prepared by powder metallurgy from a mixed powder obtained by uniformly mixing 10% by weight of a powdery antibacterial agent having the same composition and a particle size of 0.3 μm is set.

Subsequently, while flowing nitrogen as a reaction gas into the sputtering apparatus, composite plating was performed by a sputtering method, and the base material contained about 1% by weight of a powdery antibacterial agent having a particle size of 0.3 μm. A 0.3 μm thick gold-colored composite plating layer was formed to obtain a spectacle frame A2 (not shown) as an ornament.

Although not shown, when observed under a microscope, the powdered antibacterial agent was uniformly distributed in the composite plating layer and exposed to the outer surface of the composite plating layer, as in the first embodiment. It was evenly distributed in. It should be noted that this uniform distribution allows the spectacle frame to have an antibacterial property without variation.

Subsequently, the spectacle frame A2 and the spectacle frame B2 (on which the base material is plated by a sputtering method using Ti powder and then electrodeposited with the above-mentioned powdery antibacterial agent mixed paint) Sterilization rate of a conventional example (not shown) and a spectacle frame C2 (not shown) plated by a sputtering method using Ti powder without using an antibacterial agent as a base material and a sterilization rate with time. Cass test was performed to compare The results are shown in Table 2.

[Table 2]

From these results, the spectacle frame A2 and the spectacle frame B2 both had a sterilization rate of 9 before the Cass test.
Although it is 9.9%, after 24 hours of the test, the spectacle frame A2 is 99.9% which is the same as that before the test, whereas the spectacle frame B2 is lowered to 52.0%. That is, it was found that the spectacle frame A2 maintains a high sterilization rate for a long period of time as compared with the spectacle frame B2.
Also, when observing the color tone and gloss with the naked eye,
The spectacle frame A2 is comparable to the spectacle frame C2, while the spectacle frame B2 is the spectacle frame A2.
It was confirmed to be inferior to C2.

The third preferred embodiment of the present invention, which is applied to the wet plating method for eyeglass frames, will be described in detail below.

First, a 0.45 dm ² Ti wire rod is molded into a shape of an eyeglass frame to be used as a base material (not shown, see FIG. 1).

Next, in a plating solution of Au-Pd-Cu,
The same composition as the powdered antibacterial agent 7 of the first embodiment and a particle size of 0.1 μm
The powdered antibacterial agent of m is added at a rate of about 20 g / l, and the base material is set in a plating tank.

Subsequently, the plating solution was energized for 3 minutes at a current density of 0.5 A / dm ² while using both stirring and ultrasonic irradiation, and the base material was treated with a powdered antibacterial agent having a particle size of 0.1 μm. A 0.5 μm thick Au—Pd—Cu alloy composite plating layer containing about 4% by weight of the agent is formed to obtain an eyeglass frame A3.

The powdered antibacterial agent is evenly distributed in the formed composite plating layer by being uniformly dispersed in the plating solution by stirring and irradiating with ultrasonic waves. Particularly, not only in the composite plating layer but also on the outer surface. Since it is evenly distributed in the exposed state, the antibacterial activity of each part of the spectacle frame does not vary.

Subsequently, the spectacle frame A3 and the spectacle frame obtained by subjecting the base material to wet plating with a plating solution of Au-Pd-Cu and then electrodeposition coating with a paint containing the above-mentioned powdery antibacterial agent are applied. Sterilization rate of B3 (conventional example, not shown) and spectacle frame C3 (not shown) that has been wet-plated with a plating solution of Au-Pd-Cu without using an antibacterial agent for the base material and the passage of time A sterilization test was performed to compare the effective sterilization rates. In this sterilization test, the eyeglass frame was
It was performed after soaking for 4 hours. When the spectacle frame is soaked in the artificial sweat solution for 24 hours in this manner, the state becomes almost the same as that after one year in actual use. The sterilization rate was measured by the shake flask method. The test results are shown in Table 3.

[Table 3]

From these results, the sterilization rate of both the spectacle frame A3 and the spectacle frame B3 was 99.9 before the test.
%, But in the test after immersion for 24 hours, the spectacle frame A3 was 99.0%, whereas the spectacle frame B3 was sharply decreased to 18.0%.
It was found that the sterilization rate was kept high for a long period of time as compared with the spectacle frame B3. In addition, visual observation of color tone and gloss confirmed that the spectacle frame A3 was comparable to the spectacle frame C3, while the spectacle frame B3 was inferior to the quantitative frames A3 and C3.

Hereinafter, a preferred fourth embodiment of the present invention, which is applied to the wet plating method for decorative parts, will be described in detail.

First of all, it was molded into the shape of a decorative component.
A brass piece of 1 dm ² is used as a base material (not shown).

Next, in a plating solution containing 1% by weight of Au-Ni, the same composition as that of the powdery antibacterial agent 7 of the first embodiment was used, and the grain size was 0.1.
A powdered antibacterial agent of 05 μm is added at a rate of 10 g / l.

Subsequently, the plating solution is energized for 5 minutes at a current density of 1 A / dm ² while using both stirring and ultrasonic irradiation, and a powdered antibacterial agent having a particle size of 0.05 μm is applied to the base material. A containing 0.5 μm thick precious metal as a main component containing about 3% by weight
A composite plating layer, which is a u-Ti alloy plating layer, is formed to obtain a decorative part A4 (not shown).

The powdered antibacterial agent is evenly distributed in the formed composite plating layer by being uniformly dispersed in the plating solution by stirring and irradiation with ultrasonic waves. Particularly, not only in the composite plating layer but also on the outer surface. Since it is evenly distributed in the state of being exposed to the outside, it exhibits uniform antibacterial properties in each part of the spectacle frame.

Then, the above-mentioned component A4 and Au-T on the base material.
Parts B4 (conventional example, not shown) that has been subjected to wet plating with an i plating solution and then electrodeposition coated with the above-mentioned powdery antibacterial agent-mixed material, and without using an antibacterial agent as a base material Au-
A sterilization test was performed to compare the sterilization rate with the component C4 (not shown) that was wet-plated with the Ti plating solution and the sterilization rate over time. This sterilization test consists of parts A4, B4, C
4 is performed after being immersed in the artificial sweat solution for 24 hours, and when each component is immersed in the artificial sweat solution for 24 hours, the state becomes substantially the same as that after one year in actual use. The sterilizing power was measured by the shake flask method. The results are shown in Table 4.
Shown in

[Table 4]

From these results, the sterilization rate of both parts A4 and B4 was 99.9% before the test, but 24
After the test after the time immersion, the component A4 was 99.0%, whereas the component B4 showed a sharp decrease to 13.0%, and the component A4 had a sterilization rate over time as compared with the component B4. It has been found that the antibacterial property is high, that is, the high antibacterial property can be maintained for a long period of time. Further, when the color tone and gloss were visually observed, it was confirmed that the component A4 was comparable to the component C4, while the component B4 was inferior to the components A4 and C4.

Further, by using the above parts A4 and B4, Ni
When a patch test was conducted on 5 people with allergies, the results shown in Table 5 were obtained.

[Table 5]

From this result, it was found that the component A4 is less likely to cause Ni allergy than the component B4. It is considered that this is because the powdered antibacterial agent is uniformly distributed on the outer surface of the composite plating layer of the component A4, and the area where Ni in the composite plating layer directly contacts the skin is reduced. As described above, the above-mentioned fourth embodiment has another advantage of preventing Ni allergy.

A modified example of the first to fourth embodiments is a surface treatment method in which the powdered antibacterial agent used in each is replaced with a rutile type titanium oxide as a main component. And
This powdered antibacterial agent has a particle size of 1 μm or less and has a content of 0.05 μm or less in the composite plating layer as in the case of each example.
It is preferably contained in an amount of 20% by weight to 20% by weight. In addition,
The powdery antibacterial agent containing rutile titanium oxide as a main component has a characteristic that it is easy to form a small particle size.

The present invention is not limited to the above-mentioned embodiments, and for example, the inorganic carrier may be replaced with another substance other than calcium phosphate capable of substituting the antibacterial metal ion. As the antibacterial metal ion, in addition to silver, at least one selected from the group consisting of copper, zinc, tin, bismuth and chromium may be used. When silver is used as in the above-mentioned embodiment, the hardness is high, and therefore, it has a sufficient wear resistance with a thickness of a fraction of that of a normal plating layer. Therefore, a noble metal is particularly used as a plating material. In this case, it has an advantage that it is economically effective and effective.

[0047]

As described above, according to the present invention, by forming a composite plating layer in which a powdered antibacterial agent is uniformly distributed,
It is highly resistant to ultraviolet rays, sweat, abrasion, alcohol, etc., does not adversely affect the original color tone and luster of plating, and has the effect of maintaining high antibacterial properties for a long period of time.

[Brief description of drawings]

FIG. 1 is a front view of a spectacle frame.

FIG. 2 is an enlarged partial vertical sectional view of a spectacle frame.

FIG. 3 is a schematic vertical sectional view of an ion plating apparatus.

[Explanation of symbols]

 1 Base material 7 Powdered antibacterial agent 8 Composite plating layer

Claims (10)

[Claims] 1. A uniform mixture of a powdered antibacterial agent obtained by substituting a part of an inorganic carrier with an antibacterial metal ion and a plating metal are heated, and reacted with a predetermined reaction gas as necessary. A surface treatment method for an ornamental article having antibacterial properties, which comprises forming a composite plating layer in which the above-mentioned powdery antibacterial agent is uniformly distributed on a base material by an ion plating method or a sputtering method which is carried out. 2. The surface treatment method for an ornamental article having antibacterial properties according to claim 1, wherein the inorganic carrier is calcium phosphate. 3. The antibacterial metal ion is silver, copper, zinc,
The surface treatment method for a decorative article according to claim 1 or 2, which is at least one selected from the group consisting of tin, bismuth, and chromium. 4. Ion plating performed by heating a mixture of a powdered antibacterial agent containing rutile titanium oxide as a main component and a metal for plating uniformly, and reacting with a predetermined reaction gas as necessary. A surface treatment method for decorative articles having antibacterial properties, which comprises forming a composite plating layer in which the above-mentioned powdery antibacterial agent is uniformly distributed on the substrate by a sputtering method or a sputtering method. 5. The base material and the powdered antibacterial agent are applied by a wet plating method using a plating solution in which a powdered antibacterial agent obtained by substituting a part of an inorganic carrier with antibacterial metal ions is uniformly mixed. A method for surface treatment of a decorative article having antibacterial properties, which comprises forming a composite plating layer in which a metal in a plating solution is co-deposited to uniformly distribute the powdery antibacterial agent. 6. The method for surface treatment of a decorative article having antibacterial properties according to claim 5, wherein the inorganic carrier is calcium phosphate. 7. The antibacterial metal ion is silver, copper, zinc,
The surface treatment method for an ornamental article having antibacterial properties according to claim 5 or 6, which is at least one selected from the group consisting of tin, bismuth and chromium. 8. The powdered antibacterial agent and the metal in the plating solution are applied to a base material by a wet plating method using a plating solution in which a powdered antibacterial agent containing rutile titanium oxide as a main component is uniformly mixed. A surface treatment method for an ornamental article having antibacterial properties, characterized by forming a composite plating layer in which the powdery antibacterial agent is uniformly distributed by co-deposition. 9. The method according to claim 5, wherein the plating solution contains a noble metal as a main component.
Alternatively, the surface treatment method for an ornamental article having antibacterial properties according to claim 7 or claim 8. 10. The powdery antibacterial agent has a particle size of 1 μm or less, and 0.05 to 20% by weight in the composite plating layer.
%, The claim 1, the claim 2, the claim 3, the claim 4, the claim 5, the claim 6, the claim 7, or the claim 8 or The surface treatment method for an ornamental article having antibacterial properties according to claim 9.