JPH10158539A - Antimicrobial and antifungal pigment excellent in water repellency and nontackiness - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pigment having water repellency, nontackiness and antimicrobial and antifungal properties in combination. SOLUTION: This antimicrobial and antifungal pigment is prepared by forming an islandlike coating (e) of a silver alloy containing 10-50wt.% Cu and/or Zn or a nickel alloy containing 10-50wt.% Cu and/or Sn on the surface of a tetrafluoroethylene resin particle (c) according to a sputtering method. The amount of the coated silver alloy or nickel alloy is preferably regulated within the range of 0.5 20wt.% in order to expose the surface of the tetrafluoroethylene resin particle effective in water repellency and nontackiness. When the silver alloy or nickel alloy is formed as a coating layer for an amorphous phase, activities are high and greater antimicrobial and antifungal actions are manifested. The silver alloy or nickel alloy is formed as the islandlike coating (e) on the surface of the resin particle (c) to thereby expose the resin particle (c) to the surface of a coating film and/or a resin molding product. As a result, the surface to which water repellency and nontackiness derived from the tetrafluoroethylene resin and further antimicrobial and antifungal properties derived from the silver alloy or nickel alloy are imparted is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial / antifungal pigment to be added to paints and plastics in order to impart antibacterial / antifungal action to painted plates, resin molded products and the like.

[0002]

2. Description of the Related Art For interior materials, exterior materials, furniture furniture, home electric appliances, etc., a water-repellent treatment is applied to prevent stains and impart a clean feeling.
A material with a non-stick coating is used. In water-repellent processing, non-adhesive coating, etc., an ethylene tetrafluoride resin is mainly used as an active ingredient (Japanese Patent Publication No. 55-3091).
No. 0). For example, when a resin paint containing tetrafluoroethylene resin is applied to the surface of a steel plate or the like and baked,
A coating film having a two-layer structure of a surface layer in which the tetrafluoroethylene resin is concentrated and a lower layer is formed. The lower layer is mainly composed of a thermoplastic polyether sulfone resin having an aromatic hydroxyl group or the like, and secures the adhesion of the coating film to the base material. The surface layer expresses water repellency and non-adhesion by concentrating the tetrafluoroethylene resin.

In recent years, a hygienic environment has been strongly desired, and it has been studied to impart an antibacterial and antifungal action to a water-repellent or non-adhesive painted surface. Antibacterial and antifungal pigments are roughly classified into organic and inorganic pigments, and can be used depending on the application. Generally, a pigment is dispersed in paint, cement, resin, and the like. Organic pigments have problems in heat resistance, persistence of effects, safety, and the like. In addition, in a state in which the antibacterial and antifungal effects are inactivated, they may become a nutrient source and promote the propagation of various bacteria. Inorganic antibacterial and antifungal pigments are A
It utilizes the fact that metals or ions such as g, Cu, Zn, Ni, etc. exhibit an antibacterial and antifungal action. These metals are used by being supported on ceramics such as zeolite by ion exchange.

[0004]

However, in order to further impart an antibacterial and antifungal action to a material having water repellency and non-adhesiveness by concentrating the surface of a tetrafluoroethylene resin, a metal or metal ion is supported. Even if the antibacterial / antifungal agent of ceramics is added to the tetrafluoroethylene resin, the added antibacterial / antifungal agent is not included in the outermost fluororesin layer due to the specific gravity and the surface tension, and settles in the lower layer. As a result, the desired antibacterial and antifungal action cannot be imparted to the surface layer. In addition, when applied to non-adhesive painted steel sheets, it is colored black to improve stain resistance, but the conventional inorganic antibacterial agent is white, so the color change after addition may be a problem. It has become. The present invention has been devised to solve such a problem. By providing a metal antibacterial and antifungal agent as an island-shaped coating on the surface of an ethylene tetrafluoride resin, it is possible to provide water repellency and non-adhesion. It is an object of the present invention to provide a pigment that maintains antibacterial properties and imparts an antibacterial and antifungal action to a surface layer.

[0005]

In order to achieve the object, the antibacterial and antifungal pigment of the present invention forms a silver alloy or nickel alloy island-like coating layer on the surface of ethylene tetrafluoride resin particles by a sputtering method. It is characterized by doing. 10 to 50% by weight of the island-shaped coating layer acting as an antibacterial and antifungal agent
Of a silver alloy containing Cu and / or Zn or a Cu and / or Sn nickel alloy of 10 to 50% by weight on the surface of the ethylene tetrafluoride resin particles. At this time, the coating amount of the silver alloy or the nickel alloy is preferably adjusted to a range of 0.5 to 20% by weight in order to expose the surface of the ethylene tetrafluoride resin particles effective for water repellency and non-adhesion. . Further, when a silver alloy or a nickel alloy is formed as a coating layer of an amorphous phase, the activity is high and a larger antibacterial and antifungal action is exhibited. Further, since the pigment coated in this way is blackened, it can be easily applied to a black coating film, resin, artificial leather, plastic plate, film and the like.

[0006]

When a resin paint containing a tetrafluoroethylene resin is applied to the surface of a substrate and baked, a coating film a having a two-layer structure is formed on the surface of the substrate b as shown in FIG. Surface layer a _u of the coating a is tetrafluoroethylene resin particles c are is concentrated, the lower a _d through a substrate as a main component a thermoplastic polyether sulfone resin having an aromatic hydroxyl group b Adhered to. Since the resin particles c are exposed on the surface, water repellency and non-adhesiveness derived from the tetrafluoroethylene resin are exhibited. Ag, Cu, Zn, N as antibacterial and antifungal agents are added to the resin coating forming such a two-layer coating film a.
even when the antimicrobial metal d or their i such added antibacterial ceramic carrying an ion state or the like, antibacterial metal d settles in the lower layer a _d in relation to gravity and surface tension. for that reason,
The antibacterial and antifungal functions originally exhibited by the antibacterial metal d or the antibacterial ceramics carrying them in an ionic state or the like cannot be obtained.

Therefore, in the present invention, as shown in FIG. 2, a pigment f having an antibacterial and antifungal metal provided as an island-like coating e on the surface of the tetrafluoroethylene resin particles c is used. In the antibacterial / antifungal pigment f, a part of the surface of the resin particles c is coated with an antibacterial / antifungal metal, but on the remaining surface, the ethylene tetrafluoride resin is exposed. Moreover, less because at a coverage is deposited antibacterial and antifungal metal, the case of forming a coating film a shown in FIG. 1, concentrated in the same manner as the surface layer a _u a conventional tetrafluoroethylene resin particles c I do. Accordingly, the tetrafluoroethylene resin particles c effective for water repellency and non-adhesion are exposed on the surface, and the antibacterial and antifungal metal is also exposed on the surface. As described above, the surface concentration of the pigment f provided with the island-shaped coating e of the antibacterial and antifungal metal without sedimentation can be achieved by injection molding a resin compound containing the pigment f.
The same applies to a resin molded product molded by blow molding, compression molding, extrusion molding, or the like. As a result, a surface having antibacterial and antifungal effects in addition to water repellency and non-adhesiveness can be obtained.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION When used as a pigment for a coating material, the tetrafluoroethylene resin particles have a center particle diameter or a median particle diameter within a range of 1/3 to 1/10 of a film thickness to be formed. Is preferred. 10 μm for resin kneading
The following are preferred from the viewpoint of dispersibility and the like. In addition, the molecular weight is preferably relatively low, such as about 200,000 to 2,000,000 for paints, in order to improve dispersibility and workability in the paint, and about 2,000,000 to 10,000,000 for resin kneading. Is excellent in strength. As a means for forming an antibacterial / antifungal metal island coating on the tetrafluoroethylene resin particles,
A powder sputtering device developed by the present inventors can be used. In this type of powder sputtering apparatus, an apparatus for feeding powder to a rotating drum and sputtering powder particles fluidized by the rotation of the rotating drum (Japanese Patent Laid-Open No. 2-153068) is used. Sputtering equipment (Japanese Patent Laid-Open No. Sho 62)
-250172).

As shown in FIG. 3, the powder sputtering apparatus has a rotary drum 1 supported by two rolls 2 and one of the rolls 2 is rotated by a motor 3 as shown in FIG. Inside the rotating drum 1, two sputtering sources 4 are arranged, and the charged tetrafluoroethylene resin particle raw material 5 is sputtered. Above the rotating drum 1, a decompression processing chamber 7 having a heating coil 6 on its outer periphery is arranged.
The bottom of the decompression processing chamber 7 is connected to the rotary drum 1 via a supply pipe 9 provided with a valve 8. The supply pipe 9 has a double pipe structure in which an Ar gas introduction pipe 10 is inserted inside a portion below the valve 8, and is inserted into the inside of the rotary drum 1 from a side surface, and a tip of the rotary drum 1 is provided. Extends to the bottom. A branch pipe 11 is attached to the supply pipe 9 below the valve 8, and the tip of the branch pipe 11 is connected to the fluid jet mill 12. The outlet side of the fluid jet mill 12 is connected to the upper part of the decompression processing chamber 7 via the circulation pipe 13. Valves 14 and 15 are inserted into the branch pipe 11 and the circulation pipe 13, and a solid-gas separation device 16 is connected to the circulation pipe 13.

The resin particles 5 metal-coated by sputtering in the rotating drum 1 are sent from the branch pipe 11 and the circulation pipe 13 to the decompression processing chamber 7 and subjected to the sputtering process until the coating having a predetermined thickness is formed in an island shape. Served repeatedly. Here, when the amount of the antibacterial and antifungal metal adhered to the tetrafluoroethylene resin particles is adjusted to a range of 0.5 to 20% by weight, an island-like coating e partially covering the surface of the resin particles c is formed. You. If the amount of the antibacterial and antifungal metal adhered is less than 0.5% by weight, the obtained antifouling and antifungal action of the pigment f is small. Conversely, coating the antibacterial and antifungal metals deposition amount exceeds 20 wt%, the entire surface of the resin particles 5 are covered with antibacterial and antifungal metals, pigments f hardly concentrated on the surface layer a _u . Such adjustment of the amount of adhesion can be easily performed by powder sputtering. The resin particles 5 (pigment f) on which the island-shaped coating is formed are collected by the solid-gas separation device 16.

Examples of the antibacterial and antifungal metal that forms the island-shaped coating e include a silver alloy containing 10 to 50% by weight of Cu and / or Zn or a nickel alloy containing 10 to 50% by weight of Cu and / or Sn. used. Ag and Ni exhibit antibacterial properties by themselves, but when Cu, Zn or Sn is alloyed with them, a better antibacterial and antifungal action is exhibited. The content of Cu and / or Zn or Cu and / or Sn is 1
Outside the range of 0 to 50% by weight, the effect of alloying is reduced. Japanese Patent Application No. 7-294739 discloses this type of alloy.
And Japanese Patent Application No. 8-24946 are silver alloys and nickel alloys proposed by the present inventors. Among them, Cu:
10 to 50% by weight, Zn: 10 to 50% by weight, and Ag:
10 to 50% by weight or Cu: 10 to 50% by weight, Sn:
An alloy system having a composition of 10 to 50% by weight and Ni: 10 to 50% by weight exhibits an amorphous phase, and since each component is uniformly eluted and ionized over a long period of time, the antibacterial and antifungal action is maintained. Excellent in nature. The above-mentioned content is necessary for making the alloy coating amorphous.

Since the island-shaped coating e of the antibacterial and antifungal metal is formed by a sputtering method, it has a microstructure with a rapid cooling effect. Also in this respect, the elution of the antibacterial and antifungal metal elements is constant, and the effect is maintained for a long time. Above all, those that have become amorphous have little change in the elution rate of the constituent elements with time and have good corrosion resistance. Pigment f provided with antibacterial and antifungal metal island coating e
Is mixed with a paint such as a thermoplastic polyether sulfone resin having an aromatic hydroxyl group, or is made into a resin by mixing an ordinary tetrafluoroethylene resin with the pigment f. In addition, vinyl chloride, epoxy, urethane, polyethylene, etc. It is blended into resin compounds. At this time, in addition to the pigment f,
Ordinary tetrafluoroethylene resin particles can also be blended into the paint or resin compound.

[0013]

【Example】

Example 1: Production of a coated steel sheet provided with antibacterial and antifungal properties, water repellency, and non-adhesiveness In an atmosphere with an Ar partial pressure of 1 × 10 ⁻³ Torr, a particle size of 1 to 10
Ag 40% by weight, Cu3
An alloy of 0% by weight and 30% by weight of Zn was coated at a power of 500 W by a sputtering method. FIG. 4 shows appearance photographs of the resin particles subjected to the sputtering treatment with the coating amount adjusted to 10% by weight and 50% by weight, respectively. As is clear from the comparison in FIG. 4, when the coating amount is 10% by weight, the coating layer is formed in an island shape on the surface of the resin particles. On the other hand, when the coating amount is 50% by weight, the island-like coating layer is partially observed, but most of the coating layer completely covers the resin particle surface. These two kinds of antibacterial and antifungal metal-coated ethylene tetrafluoride resins are mixed with 10% by weight of uncoated ethylene tetrafluoride resin and mixed with 50% by weight of a thermoplastic polyether sulfone resin having an aromatic hydroxyl group. This was applied to a galvanized steel sheet and baked.

The obtained coating film was analyzed by EPMA. As shown in FIG. 5 showing the analysis results, it is understood that the coating with 10% by weight of the antibacterial and antifungal metal is concentrated in the outermost surface layer. On the other hand, in the case of the 50% by weight coating, a part of the outermost surface layer is thickened, but the sedimentation in the lower layer is also confirmed. Ag 40% by weight-Cu30 at various coverages
% By weight-30% by weight of Zn and 40% by weight of Ni-Cu30
% By weight of an alloy having a composition of 30% by weight of Sn and 30% by weight of a pigment prepared by mixing 5% of the uncoated tetrafluoroethylene resin with 70% by weight of an aromatic hydroxyl group. It was mixed with a plastic polyether sulfone resin and painted on a galvanized steel sheet. The relationship between the coating amount of the obtained coating film and water repellency (non-adhesiveness) and antibacterial and antifungal properties was investigated. The water repellency (non-adhesiveness) was determined by adding 10 cc of a mixture of egg, sugar and soy sauce at a weight ratio of 1: 1: 1 to a coated steel plate, heating at 250 ° C. for 60 minutes,
Evaluation was made on the state of remaining on the coating film when peeled.

FIG. 6 shows the results of the investigation. In FIG. 6, ◎ indicates that each property is particularly excellent, ○ indicates that the property is excellent, and X indicates that no significance is observed or the property is deteriorated.
It was expressed by. As shown in FIG. 6, the coating amount was 60% by weight.
Until then, the water repellency (non-adhesiveness) is superior to that of a galvanized steel sheet shown as a comparative material coated with only a thermoplastic polyether sulfone resin having an aromatic hydroxyl group. When the coating amount is less than 0.5% by weight, antibacterial and antifungal properties are not exhibited. And
It was found that both water repellency (non-adhesiveness) and antibacterial and antifungal properties were excellent especially when the coating amount was in the range of 0.5 to 20% by weight. Tables 1 and 2 show the antibacterial and antifungal properties of pigments in which various metals were coated on a tetrafluoroethylene resin in an amount of 5% by weight, and the pigment 40 in which the coating resin was mixed in an uncoated ethylene fluoride resin in an amount of 5% by weight. 6% by weight of thermoplastic polyether sulfone resin having aromatic hydroxyl groups
It is the result which summarized the water repellency and non-adhesion when it mixes to 0 weight% and paints on a galvanized steel plate. From the results in Tables 1 and 2, when the alloy was coated under the conditions specified in the present invention,
It can be seen that each of them is excellent in both antibacterial and antifungal properties and water repellency (non-adhesiveness).

[0016]

[0017]

Ag 40% by weight-Cu 30% by weight-Zn3
A crystalline structure in which a 0 wt% alloy is coated with 5 wt% of a tetrafluoroethylene resin at an output of 600 W;
FIG. 7 shows the results of investigating the elution amount of constituent metal ions when 1 g of each of the amorphous structures indirectly cooled with W was immersed in 100 cc of boiling water. Under the same conditions, Ni 40% by weight-Cu 30% by weight-Sn 30
FIG. 8 shows the elution amount of a 5% by weight alloy coated with 5% by weight of an ethylene tetrafluoride resin. From FIGS. 7 and 8, it can be seen that when the structure of the surface coating alloy is amorphous, the elution of the constituent metals evolves quickly and the elution rate is almost constant.
On the other hand, in the case of crystalline, the elution rate fluctuated. From this comparison, it is confirmed that the amorphous structure exhibits an antibacterial and antifungal action that is superior to the crystalline structure in terms of rapidity and durability.

Example 2: Ag 40% by weight-Cu 30% by weight-Zn
30% by weight and Ni 40% by weight-Cu 30% by weight-Sn
30% by weight of the alloy was coated by sputtering. 10% by weight of these two kinds of antibacterial and antifungal metal-coated ethylene tetrafluoride resins are added to the uncoated ethylene tetrafluoride resin, and 10% by weight thereof is added to the polypropylene resin. 5 mm plates were produced. FIG. 9 shows the results of investigating the relationship between the coating amount and the water repellency (non-adhesiveness) and the antibacterial and antifungal properties in this case. The evaluation in the figure indicates that each of the properties is particularly excellent.
Those that were excellent were indicated by ○, and those that were not significant or deteriorated were indicated by x. As can be seen from FIG. 9, up to a coating weight of 80% by weight, the water repellency (non-adhesiveness) is superior to that of a plate containing only the resin not containing the ethylene tetrafluoride resin shown as a comparative material. It turns out that there is. When the coating amount was less than 0.5% by weight, antibacterial and antifungal properties were not exhibited. Water repellency (non-adhesiveness) and antibacterial and antifungal properties were both excellent when the coating amount was in the range of 0.5 to 20% by weight.

Tables 3 and 4 show antibacterial and antifungal properties of pigments coated with 5% by weight of ethylene tetrafluoride resin with various metals, and pigments with 10% by weight of coating resin mixed with uncoated tetrafluoroethylene resin. Is added to polypropylene resin by 10% by weight,
The result which summarized the water repellency (non-adhesiveness) at the time of injection molding is shown. From the results in Tables 3 and 4, it can be seen that when the alloy was coated under the conditions specified in the present invention, all were excellent in both antibacterial and antifungal properties and water repellency (non-adhesive).

[0021]

[0022]

[0023]

As described above, the pigment of the present invention is formed on the surface of the tetrafluoroethylene resin particles as an island-like coating of a silver alloy or a nickel alloy exhibiting antibacterial and antifungal properties. Therefore, when manufacturing paint films and resin molded products by blending it with paints and resin compounds, the tetrafluoroethylene resin particles coated with silver alloy or nickel alloy are exposed on the surface, and are water-repellent, non-adhesive, antibacterial, A surface with anti-fungal properties is obtained.

[Brief description of the drawings]

Fig. 1 Coating film with concentrated surface of ethylene tetrafluoride resin particles

Fig. 2 Tetrafluoroethylene resin particles with island-shaped coating of antibacterial and antifungal metal

Fig. 3 Powder sputtering equipment used to form a coating of antibacterial and antifungal metal

FIG. 4 is a photograph showing the particle structure of an ethylene tetrafluoride resin coated with an Ag—Cu—Zn alloy in Example 1.

FIG. 5 is a photomicrograph showing an EPMA composition analysis result of an Ag element in a cross section of a coating film formed from a resin paint containing an ethylene-tetrafluoroethylene resin coated with an Ag—Cu—Zn alloy in Example 1.

FIG. 6 shows an Ag—Cu—Zn alloy and Ni—
Graph showing antibacterial and antifungal properties and water repellency (non-adhesive) when a tetrafluoroethylene resin coated with a Cu-Sn alloy is applied

FIG. 7 is a graph showing the elution amount of metal ions in boiling water of an ethylene-tetrafluoroethylene resin coated with an Ag—Cu—Zn alloy in Example 1.

FIG. 8 is a graph showing the elution amount of metal ions in boiling water of a tetrafluoroethylene resin coated with a Ni—Cu—Sn alloy in Example 1.

FIG. 9 shows an Ag—Cu—Zn alloy and Ni—
Graph showing antibacterial and antifungal properties and water repellency (non-adhesive) of a plate obtained by injection molding from a polypropylene resin mixed with a tetrafluoroethylene resin coated with a Cu-Sn alloy.

[Explanation of symbols]

a: coating film _au : surface layer _ad : lower layer b: substrate c: ethylene tetrafluoride resin particles d: antibacterial metal e: island-like coating of antibacterial / antifungal metal f: antibacterial / antifungal metal Pigment with island-shaped coating of 1: Rotary drum 2: Roll 3: Motor 4:
Sputtering source 5: Raw material of resin particles 6: Heating coil 7: Decompression processing chamber 8: Valve 9: Supply pipe 10: Ar gas introduction pipe 11: Branch pipe 12: Fluid jet mill 13: Circulation pipe 1
4, 15: valve 16: solid-gas separation device

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[Procedure amendment]

[Submission date] November 29, 1996

[Procedure amendment 1]

[Document name to be amended] Drawing

[Correction target item name] Fig. 4

[Correction method] Change

[Correction contents]

FIG. 4

[Procedure amendment 2]

[Document name to be amended] Drawing

[Correction target item name] Fig. 5

[Correction method] Change

[Correction contents]

FIG. 5

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08K 9/02 C08K 9/02 C09D 5/14 C09D 5/14 (72) Inventor Hiroshige Nakamura 7th Takatani Shinmachi, Ichikawa City, Chiba Prefecture No. 1 Inside Nisshin Steel R & D Co., Ltd. (72) Inventor Akira Takeshima No. 7-1 Takaya Shinmachi, Ichikawa-shi, Chiba Nisshin Steel R & D Co., Ltd.

Claims (5)

[Claims] 1. An antibacterial / antifungal pigment excellent in water repellency and non-adhesiveness, wherein an island-shaped coating layer of a silver alloy or a nickel alloy is formed on the surface of tetrafluoroethylene resin particles by a sputtering method. 2. A silver alloy comprising 10 to 50% by weight of Cu and / or
The antibacterial and antifungal pigment according to claim 1, which is an alloy containing Zn or Zn. 3. The method according to claim 1, wherein the nickel alloy comprises 10 to 50% by weight of Cu.
The antibacterial / antifungal pigment according to claim 1, which is an alloy containing and / or Sn. 4. The antibacterial and antifungal pigment according to claim 1, wherein the silver alloy or the nickel alloy exhibits an amorphous phase. 5. The antibacterial / antifungal pigment according to claim 1, wherein the coating amount of the silver alloy or the nickel alloy to the tetrafluoroethylene resin particles is 0.5 to 20% by weight.