JP2003245132A - Antibacterial goods or toothbrush containing inorganic antibacterial agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antibacterial toothbrush effectively preventing the propagation of various bacteria in the oral cavity. <P>SOLUTION: The antibacterial goods or the antibacterial toothbrush contains an inorganic antibacterial agent containing a zinc ion and a metal salt of a carboxylic acid with five or more carbons, or contains an inorganic antibacterial agent containing an oxide or a hydroxide of at least one kind of metal element chosen from an alkali metal, an alkaline earth metal, titanium, zirconium, aluminum, or silicone and a zinc ion. The antibacterial goods or tooth brush has sufficient antibacterial effect, and sufficient persistence of the effect (especially the persistence of not losing effect even when soaked in tap water for long time), moreover the antibacterial goods or the antibacterial toothbrush does not have any weak point of discoloring or the like. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial product and an antibacterial toothbrush that are safe and have an antibacterial effect maintained for a long period of time.

[0002]

2. Description of the Related Art Toothbrushes are used in the oral cavity and are required to be clean, but it is quite difficult to keep them clean. That is, frequent sterilization after use is not usually performed. After using the toothbrush, storing the toothbrush in a washbasin cabinet or a carrying case in a damp state causes insufficient drying, and various bacteria, such as mold, easily propagate. To solve these problems, various antibacterial toothbrushes have been proposed. For example, JP-A-6-22818 and JP-A-10-5044 describe antibacterial toothbrushes obtained by kneading zinc oxide or the like into a synthetic resin. However, when the zinc oxide particles are kneaded into the synthetic resin, the zinc oxide particles tend to agglomerate and reduce the total surface area, resulting in an insufficient antibacterial effect. Further, zinc oxide easily dissolves when immersed in a slightly acidic aqueous solution, which has a drawback that the antibacterial effect is rapidly lost. Therefore, the antibacterial toothbrush using these zinc compounds has an insufficient antibacterial effect, and rapidly loses the antibacterial effect when exposed to slightly acidic tap water for a long period of time. In addition, organic antibacterial agents that have been used for some time have recently tended to be refrained from use because of their safety (sick house syndrome, etc.), and they have the drawback that the antibacterial effect does not continue. Furthermore, the silver-based antibacterial agents that have been used in recent years have not only an insufficient antibacterial effect, but also a drawback of reacting with chlorine ions in tap water to lose the antibacterial effect and a drawback of being colored by light, which is not preferable. Therefore, there is a demand for an antibacterial toothbrush or an antibacterial product which is easy to be kneaded into a synthetic resin, is safe, has a long-term antibacterial effect even when exposed to various use conditions, and has no drawbacks such as coloring. .

[0003]

As described above, the conventional antibacterial toothbrush has a large antibacterial effect, sustainability of the effect (especially persistence in which the antibacterial effect is not lost even when exposed to tap water for a long time). Not only was the safety insufficient, but it also had drawbacks such as coloring. An object of the present invention is to provide an antibacterial product or an antibacterial toothbrush which solves the above-mentioned conventional problems.

[0004]

[Means for Solving the Problems] In order to solve the above-mentioned problems and the like and to achieve the above-mentioned objects, an antibacterial product or an antibacterial toothbrush according to claim 1 of the present invention is an inorganic system containing zinc ions. At least one metal salt of an antibacterial agent and a fatty acid having 5 or more carbon atoms, a resin acid and naphthenic acid
It is characterized by containing a metal salt of a seed. An antibacterial product or an antibacterial toothbrush according to claim 2 of the present invention is an oxide or hydroxide containing at least one of alkali metal, alkaline earth metal, titanium, zirconium, aluminum and silicon and a zinc ion. It is characterized by containing a certain inorganic antibacterial agent. The antibacterial product or the antibacterial toothbrush according to claim 3 of the present invention is an oxide or hydroxide containing at least one of alkali metal, alkaline earth metal, titanium, zirconium, aluminum and silicon and zinc ion. It is characterized by containing at least one metal salt of an inorganic antibacterial agent and a metal salt of a fatty acid having 5 or more carbon atoms, a resin acid and naphthenic acid.

The metal salts of fatty acids having 5 or more carbon atoms, resin acids and naphthenic acids used in the present invention are not particularly limited, but the following are used. Of these, metal salts of fatty acids are preferred.

As the fatty acid, either saturated fatty acid or unsaturated fatty acid is used. Examples include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, ricinoleic acid, 2-ethylhexanoic acid, ricinoleic acid, and isodecanoic acid. . Resin acids include abietic acid, neoabietic acid, d-bimalic acid, and cinnamic acid. Among these, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid,
Ricinoleic acid is preferred.

Examples of the metal include alkali metal, alkaline earth metal, transition metal and the like. Alkali metals include lithium, sodium, potassium and cesium, alkaline earth metals magnesium, calcium, barium,
Zinc is preferred as the transition metal. Of these, zinc is preferred.

As specific examples, zinc stearate, barium stearate, calcium stearate, magnesium stearate, zinc laurate, barium laurate, calcium laurate, magnesium laurate,
Examples include calcium ricinoleate, barium ricinoleate, and zinc ricinoleate. Of these, zinc compounds are preferable, and zinc stearate, zinc laurate, and zinc ricinoleate are particularly preferable.

As the inorganic antibacterial agent of the present invention, any compound containing zinc is preferable. For example, inorganic zinc compounds such as zinc oxide, zinc sulfate, zinc chloride, zinc phosphate, zinc nitrate and zinc carbonate, and organic zinc salts such as zinc acetate, zinc oxalate, zinc citrate, zinc fumarate and zinc formate are used. Can, alkali metal, alkaline earth metal, titanium,
At least one of zirconium, aluminum and silicon
There are oxides or hydroxides containing seeds and zinc ions. More preferred are oxides or hydroxides containing at least one of alkali metals, alkaline earth metals, titanium, zirconium, aluminum and silicon and zinc ions. More preferably, these oxides and hydroxides are solid solutions. Among these, Na and K are more preferable as the alkali metal, and Mg and Ca are more preferable as the alkaline earth metal. Oxides are more preferable than hydroxides.

Further, those represented by the following formulas (1) to (6) are more preferable, and the following formulas (1), (4) and (5)
Is more preferable. (1) is the most preferable. Zn _x N _1-x O (1) (wherein N represents Mg and / or Ca, and x is 0.02 <x <0.8) Zn _y N _1-x (OH) ₂ (2 (In the formula, N and x are the same as those in the formula (1)) (ZnO) · (L ₂ O) _y (3) (In the formula, L represents an alkali metal ion and y is 0.00
01 <y <0.1) (ZnO) · (Al ₂ O ₃ ) _a · (SiO ₂ ) _b (4) (where a is 0.00 ≦ a <50 and b is 0.00 ≤b <
80. However, when a = 0, b is 0.001 ≦
When b <80 and b = 0, a is 0.001 ≦ a <
50. ) (ZnO). (XO ₂ ) _c (5) (In the formula, X represents Ti and / or Zr.
It represents 001 <c <0.2. ) (ZnO) · (NO) _d · (Al ₂ O ₃ ) _e (6) (In the formula, N is the same as the formula (1). D is 0.05 ≦ d <5.
And b is 0.01 ≦ b <5. ) Mg in the formulas (1) and (2) is more preferably Mg. It is preferable that L in the above formula (3) is Na or K. In addition, a and b in the above formula (4)
Is more preferably a is 0.00 ≦ a <2 and b is 0.0
0 ≦ b <50 (however, when a = 0, b is 0.
When 001 ≦ b <50 and b = 0, a is 0.00
1 ≦ a <2). More preferably, a is 0.00 ≦
a <0.2 and b is 0.00 ≦ b <1 (however,
When a = 0, b is 0.001 ≦ b <1 and b = 0
In the case of, a is 0.001 ≦ a <0.2).

Examples of preferable inorganic antibacterial agents of the present invention are shown below, but the invention is not limited thereto.
Numbers in parentheses are BET surface area (m ² / g),
The particle size D50% (μm) and the Zn content (% by weight) are shown. (1) Formula (A-1) Zn _0.14 Mg _0.86 O (50, 0.05, 1
9.9) (A-2) An antibacterial agent in which the surface of A-1 is modified with sodium laurate (50, _0.05, 19.9) (A-3) Zn _0.05 Ca _0.95 O (30, 0.08) 1
9.9) (2) Formula (A-4) Zn _0.14 Mg _0.86 (OH) ₂ (19,0.
1, 19.6) (3) Formula (A-5) ZnO. (K ₂ O) _0.005 (12
0, 0.1, 80) (A-6) ZnO. (Na ₂ O) _0.005 (9
0, 0.06, 80) (4) Formula (A-7) ZnO. (Al ₂ O ₃ ) _0.04 (30, 0.0
5, 76.5) (A-8) Antibacterial agent obtained by modifying the surface of A-7 with sodium laurate (30, _0.05 , 76.5) (A-9) ZnO. (SiO ₂ ) _0.05 (25,
0.1, 77.5) (5) Formula (A-10) ZnO. (TiO ₂ ) _0.05 (1
5,0.06,76.6) (6) _{(A-11) ZnO · (} MgO) 1.5 · (Al 2 O 3)
_1.25 (60, 0.3, 24.3)

The inorganic antibacterial agent of the present invention is preferably surface-treated. The following is an example of one that is preferably used as the surface treatment agent. Higher fatty acids having 10 or more carbon atoms such as stearic acid, erucic acid, palmitic acid, lauric acid and behenic acid; alkali metal salts of the higher fatty acids; sulfuric acid ester salts of higher alcohols such as stearyl alcohol and oleyl call; polyethylene glycol ether Sulfate ester salt, amide bond sulfate ester salt, ester bond sulfate ester salt, ester bond sulfonate, amide bond sulfonate, ether bond sulfonate, ether bond alkyl allyl sulfonate, ester bond alkyl allyl sulfonate, amide Anionic surfactants such as bound alkylallyl sulfonates; mono- or diesters of orthophosphoric acid and oleyl alcohol, stearyl alcohol, etc., or a mixture of both, in their acid form or alkali metal salt or acid Phosphoric acid esters such as emissions salt; vinyl triethoxysilane,
Vinyl-tris (2-methoxy-ethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, beta (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltri Silane coupling agents such as methoxysilane and gamma-mercaptopropyltrimethoxysilane; isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate,
Titanate coupling agents such as isopropyl tridecylbenzene sulfonyl titanate; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; esters of polyhydric alcohols and fatty acids such as glycerin monostearate and glycerin monooleate.

Of these, a surface treatment selected from the group consisting of higher fatty acids, anionic surfactants, phosphoric acid esters, coupling agents (silane-based, titanate-based, aluminum-based) and esters of polyhydric alcohols and fatty acids. Surface treatment with at least one of the agents is preferable, and higher fatty acids having 10 or more carbon atoms such as stearic acid, erucic acid, palmitic acid, lauric acid, and behenic acid, and alkali metal salts of the higher fatty acids are particularly preferable. The surface treatment can be performed by a method similar to the method described in Example 1 of JP 2001-123071A.

The particle size D50% of the inorganic antibacterial agent of the present invention is preferably 0.05 to 20 μm, more preferably 0.05 to 10 μm, and further preferably 0.05 to 5 μm. The particle size is ultrasonically dispersed for 5 minutes or more,
It is the value measured by the laser scattering method. The BET surface area of antibacterial agents is an important indicator. Generally, an extremely large BET surface area is preferable in order to rapidly exert an antibacterial effect. However, on the other hand, in order to maintain the antibacterial effect, it is necessary to set the value below a certain level. Therefore, the BET surface area is preferably 1 to 300 m2 / g, more preferably 5 to 150 m2 / g, and further preferably 10 to 150 m2 / g. Methods for producing these inorganic antibacterial agents include JP-A-6-72816, JP-A-6-65011, and JP-A-8-
-291011, JP-A-8-48606, JP-A-1
1-123385, JP-A-11-180808, JP-A-11-209258, 2000-63219.
The method described in No. can be used.

Examples of resins used include thermoplastic synthetic resins and thermosetting synthetic resins. As the thermoplastic synthetic resin, for example, fluorocarbon resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, polypropylene resin, polyolefin resin such as polyethylene resin, epoxy resin, polyacetal resin, polyester resin, polyetherimide resin, poly Ether sulfone resin, polyether ether ketone resin, polyphenylene sulfide resin, polysulfone resin, polyarylate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polymethylpentene resin, A
There are BS resin, vinyl acetate resin, polystyrene resin and the like.

Examples of the thermosetting synthetic resin include melamine resin, phenol resin, urea resin, furan resin, alkyd resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicon resin, polyurethane resin, polyimide resin. , Polyparabanic acid resin, and the like. Natural polymer resins are also included.

As the material of the polymer structure of the present invention, any of the above materials can be used, and of these, a thermoplastic resin is preferable. Among them, polyolefin resin, polyamide resin and polyethylene terephthalate resin are preferable, and polyethylene (P
E), polypropylene (PP), polyethylene terephthalate (PET) and polyamide (nylon) are particularly preferable.

[0018]

Example 1 Next, the present invention will be described in more detail with reference to examples. H- (number) indicates the sample of the present invention, C-
(Numerals) represent comparative example samples. To 70 parts of low-density polyethylene, 30 parts of a mixture of zinc stearate having a weight ratio of 2: 8 and an inorganic antibacterial agent A-1 was mixed and mixed with a mixer to obtain a 40 mm extruder (L / D = 28, C). R.
= 3.1, screw with dullage, cylinder temperature 1
Kneading at 30 ° C., screw rotation speed 80 rpm),
Pellets having a particle size of about 2 mm were prepared. Next, 60 parts of the above pellets and 640 parts of 610-nylon (manufactured by Toray) are mixed, spun and stretched by an ordinary spinning machine to have a thickness of 0.5.
mm nylon filament was prepared and cut into a length of 11 mm (H-1). Further, a polypropylene resin was kneaded with 1% by weight of an inorganic antibacterial agent A-2, and then extruded into a handle shape to prepare a handle portion of a toothbrush (H
-2). Further, H-1 and H-2 were repeated, respectively, except that the inorganic antibacterial agent and zinc stearate were not used, to prepare a comparative example filament (C-1) and a handle portion (C-2). The nylon filaments H-1, C-1 and the handle parts H-2, C-2 were sterilized in an autoclave under the conditions of 120 ° C, 1.2 atmospheric pressure and 15 minutes, and then Escherichia coli was adhered to them, and the relative temperature was 37 ° C. After leaving it for 4 days under the condition of a humidity of 80%, the number of E. coli was examined. In H-1 and H-2, the viable cell count was 1/1000 or less of the adhered number, but C-1 and C-2
-2, the viable cell count was 10 to 100 times the adhered amount. The sample using the carboxylic acid metal salt of the present invention and the inorganic antibacterial agent was preferable because the number of E. coli was smaller than that of the comparative example.

[0019]

Example 2 Moisture content 0.2-1.3%, average particle size 0.05 μm
H-1 was repeated except that the above zinc oxide powder was used instead of the inorganic antibacterial agent A-1, to obtain a filament H-3.
H-3 was repeated except that zinc stearate was not used to obtain a comparative filament C-3. H-1,3,
After immersing C-1 and 3 in tap water having a pH of 5.6 at 25 ° C for 10 days, sterilization was performed in an autoclave in the same manner as in Example 1, and Escherichia coli was adhered to the cells under conditions of 37 ° C and 80% relative humidity. After standing for 4 days, the number of E. coli was examined. The number of remaining E. coli viable bacteria is 0, and in H-1 1/1000 or less,
H-3 was 1/50, C-3 was 2 times, and C-1 was 10 times or more. The fatty acid metal salt of the present invention and the inorganic antibacterial agent A-1
H-1 used was the most preferred because it had the least E. coli. H-3 using zinc oxide and zinc stearate has a smaller number of Escherichia coli than the comparative example and is preferable, but the antibacterial effect is inferior to that of H-1.

[0020]

Example 3 An inorganic antibacterial agent was replaced by A- instead of A-1.
Example 1 except that 2, 7, 8, 9, and 10 were used, respectively.
Was repeated to obtain filaments H-4,5,6,7,8. These samples were tested for Escherichia coli as in Example 1, and the result was that the number of bacteria was 1/1000 or less as in H-1. All were favorable results as compared with Comparative Examples C-1 and C-3.

Claims (3)

[Claims] 1. An antibacterial product or antibacterial toothbrush containing at least one inorganic antibacterial agent containing zinc ions and a fatty acid having 5 or more carbon atoms, a resin acid and a metal salt of naphthenic acid. 2. An inorganic antibacterial agent which is an oxide or hydroxide containing at least one selected from alkali metals, alkaline earth metals, titanium, zirconium, aluminum and silicon and zinc ions. Antibacterial toothbrush to do. 3. An inorganic antibacterial agent, wherein the inorganic antibacterial agent is an oxide or hydroxide containing at least one of alkali metal, alkaline earth metal, titanium, zirconium, aluminum and silicon and zinc ion. The antibacterial product or the antibacterial toothbrush according to claim 1, which is characterized by being present.