JPH08325435A - Antibacterial melamine resin molding powder and molded article obtained therefrom - Google Patents

Abstract

PURPOSE: To obtain a molding resin powder capable of imparting excellent antibacterial properties to a molded amine resin article. CONSTITUTION: This powder is a molding amine resin powder containing at least one calcium ceramic selected from among calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite each having at least one antibacterial metal supported thereon as an antibacterial agent. The metal is preferably a combination of silver and at least either of zinc and copper.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial amino resin molding powder and molded articles thereof, and more specifically to calcium phosphate, carbonic acid carrying an antibacterial metal as an antibacterial agent, particularly for melamine resins. 1 or 2 selected from calcium, calcium silicate and hydroxyapatite
Melamine-based resin (including melamine resin and resin in which melamine resin and other resins are co-condensed) mixed with one or more kinds of calcium-based ceramics, molded powder and molded product thereof
And a manufacturing method thereof.

[0002]

2. Description of the Related Art Generally, plastics were considered to be substances having resistance to microorganisms such as molds and bacteria, but recently damages by those microorganisms have been reported, and antimicrobial treatment depending on their use. Came to be needed. As an antimicrobial treatment, addition of fungicides and bactericides to plastics can be considered.
In No. 4377, in order to prevent the growth of molds and pathogenic microorganisms on the surface of the synthetic resin tableware, alkylbenzene sulfonic acid was added to the surface or the inside and the surface of the tableware.
An organic compound such as a reaction mixture obtained by heating and reacting with a 6-dichloropyridazine and / or a 3-chloro-6-methylpyridazirine derivative is contained.

Up to now, as a bactericide for plastics, generally, an organic compound is generally used as in the above example, but the organic compound is weak against heat and deteriorates at the processing temperature of the plastic to lose its bactericidal property. Therefore, it is difficult to use organic germicides for plastic processing. Therefore, it has been studied and developed to impart an antimicrobial property to plastics by using an inorganic bactericide in which an antibacterial metal is supported on an inorganic substance instead of the organic bactericide.

For example, in Japanese Unexamined Patent Publication No. 62-241939, a metal having a bactericidal action on a polyolefin resin molding, specifically, one selected from the group consisting of silver, copper, zinc and tin, or A polyolefin resin having antibacterial and fungicidal ability, specifically a molded product of polyethylene and polypropylene, which contains a zeolite having two or more metals held therein, is disclosed.
In No. 4962, in a cleaning tank or a hot water tank made of a thermoplastic resin, a carrier such as zeolite, activated carbon, silica gel or clay is adsorbed and dried as an aqueous solution or colloid on a carrier such as zeolite, activated carbon, silica gel or clay. It has been proposed to mix and disperse.

In addition to this, zeolites used as the carrier are Japanese Examined Patent Publication No. 63-54013, Jikkaihei 1
-117264, Actual Kaihei 3-85965, Actual Kaihei 3
-129373, etc. Of which, Japanese Examined Japanese Patent Publication No. 63-54
In No. 013, it can be used except zeolite having a large SiO ₂ / Al ₂ O ₃ molar ratio called molecular sieve among zeolites, and in No. 1-117264, a metal having an antibacterial action, specifically, Proposes a disposable cup made of a resin, which contains an antibacterial zeolite carrying silver, copper or zinc by ion exchange in the range of 0.1 to 5% by weight.

[0006] Actual Kaihei 3-85965 and Actual Kaihei 3
In No. 129373, in addition to zeolite, inorganic compounds such as activated carbon, silica gel, and alumina are listed in the same column, and in JP-A-5-140331, an antibacterial effect is obtained by mixing zinc oxide fine particles with plastic.
It is described that it imparts antifungal and deodorant functions. Furthermore, in JP-A-3-84066, in addition to inorganic particles such as titanium oxide and silicon oxide, as particles for supporting at least one metal selected from silver, copper, zinc, gold and platinum and / or its oxide, It is said that organic particles such as polytetrafluoroethylene and polystyrene can also be used.

Furthermore, Japanese Utility Model Publication No. 2-144573 describes an antibacterial resin container containing a soluble glass powder containing Ag or Cu ions, and is disclosed in Japanese Examined Patent Publication No.
No. 68935 discloses a tableware in which a soluble glass containing Ag ions is dispersed and retained in at least the surface layer, but both of them are one system in that the soluble glass is used for supporting an antibacterial metal. It can be said that it is doing.

In addition, in Japanese Patent Laid-Open No. 4-275370,
General formula Ag _{a Ab} M ² _c (PO ₄ ) _d · nH ₂ O (wherein A:
At least one ion selected from alkali metal ions, M ² : tetravalent metal, 0 ≦ n ≦ 6, a, b: a positive number,
c, d: when a + mb = 1, c = 2, d = 3, a + mb
= 2, c = 1, d = 2, where m is the valence of A), an antibacterial resin composition comprising an antibacterial agent composed of a silver-containing phosphate compound and a resin has been proposed. Further, in JP-A-6-136137, a calcium phosphate compound which is also a phosphate compound is used for supporting the same.

[0009] According to the above proposals, these inorganic antibacterial agents are used for supporting antibacterial metals, such as inorganic compounds, especially zeolites and soluble glasses. It is carried,
These antibacterial agents are mixed and contained in plastic.
However, in such a technique, (1) the antibacterial action is still extremely weak or has no long-term sustainability, (2) discoloration due to the elution of Ag is observed, (3) swelling occurs after a boiling test for about 15 hours, for example. Not only are the antibacterial properties and persistence difficult to occur, for example, but the characteristics of the molded article itself, such as swelling, are not always sufficient.

Among these techniques, Japanese Patent Laid-Open No. 3-84
No. 066 says that organic particles such as polytetrafluoroethylene and polystyrene can also be used.
No. 144573 and Japanese Patent Publication No. 4-68935 use a soluble glass which is a ceramic itself, but in the techniques described in the above-mentioned publications other than these, all use an inorganic substance as it is. However, it is not applied as ceramics by firing it.

On the other hand, in the above publication, as a general example of the types of plastics, there is one in which a thermosetting resin is also listed (Japanese Patent Publication No. 4-689).
35, JP-A-4-275370, JP-A-5-140.
No. 331, JP-A-6-136137) and the examples or specific examples described in these publications are all directed only to thermoplastic resins such as polypropylene and nylon, and are thermosetting resins such as amino resins. No specific example is found when applied to.

By the way, the present inventors do not use such an inorganic compound, one of the zeolites, or soluble glass as a carrier for an antibacterial metal selected from silver, copper, and zinc. Calcium-based ceramics,
That is, by firing a calcium compound selected from calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite to use as a ceramic, there is no elution of Ag, and a polyolefin system having excellent antibacterial and antifungal properties is provided. A resin molding was previously developed and filed (Japanese Patent Application Laid-Open No. 4-142349).

In the invention of JP-A-4-142349, the antibacterial metal is supported on the calcium-based ceramic in such a manner, and is incorporated into the polyolefin-based resin, that is, the thermoplastic resin. It is possible to obtain excellent effects such as imparting antifungal properties and preventing elution of Ag. However, the present inventors have found that an antibacterial agent composed of calcium-based ceramics carrying an antibacterial metal is treated with such heat treatment. While many studies have been conducted on the suitability of applying this to thermosetting resins, not to plastic resins, and the various conditions when applying this, while researching the They have found that they can be effectively applied to resins, especially melamine resins, and can impart excellent antibacterial and antifungal properties.

[0014]

That is, according to the present invention, an antibacterial agent composed of calcium-based ceramics carrying an antibacterial metal is used as an amino resin (in addition to melamine resin, urea, thiourea, guanidine, acetoguanamine, benzoguanamine, etc.). Amino resin molded powder which is applied to each resin alone or including co-condensed resin and is mixed with this antibacterial agent in amino resin powder, and a molded product molded from this amino resin molded powder (molding) Products) and a method for producing them.

[0015]

The present invention is an amino resin molding powder, which is selected from calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite in which the resin powder is loaded with an antibacterial metal as an antibacterial agent. An amino resin molding powder characterized by being mixed with one or more calcium-based ceramics,
In addition, an amino resin molded powder mixed with one or more calcium-based ceramics selected from calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite supporting an antibacterial metal as an antibacterial agent. Provided is an amino-based resin molded article characterized by being formed by molding a resin-based resin molding powder.

Further, the present invention relates to an amino resin molded body, an amino resin in a glaze layer thinly coated on the surface thereof, an amino resin impregnated into a monochromatic coloring paper which is the surface layer thereof, or An amino-based resin molded article having an amino-based resin impregnated into its surface layer, which is a decorative print,
The surface of the amino resin is characterized by containing one or more calcium-based ceramics selected from calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite supporting an antibacterial metal. The present invention provides an amino resin molded product having a coating layer, a monochromatic colored paper or a decorative print.

As an example of these, the case of a melamine resin decorative board will be described. In this decorative board, paper, melamine resin or phenol resin is usually used as its substrate, and one surface layer thereof is a monochromatic colored paper. Alternatively, it is composed of a decorative print impregnated with a melamine resin. Most of the lower layer of the surface layer is formed by stacking papers impregnated with phenolic resin. Of these, particularly in the case of a so-called post-home decorative plate which can be bent later. In some cases, an aniline-modified phenolic resin is used for the phenolic resin layer, but in the present invention, the above-mentioned constitution is applied to these glaze layer, monochromatic coloring paper or decorative print. It is a thing.

The present invention also provides an antibacterial metal containing at least silver and containing copper and / or zinc, calcium phosphate,
A calcium-based compound selected from calcium carbonate, calcium silicate, and hydroxyapatite was supported, the compound was fired at a temperature of 800 ° C. or higher, and then pulverized to an average particle size of 10 μm or less, and the resulting calcium-based ceramic was finely divided. Provided is a method for producing an amino resin molding, which comprises mixing a powder and an amino resin so that the content of the fine powder is at least 0.03% by weight.

Here, as the above-mentioned amino resin in the present invention, aniline aldehyde resin, urea resin and melamine resin which are resins obtained by the condensation reaction of a compound containing an amino group and an aldehyde are used, and particularly preferably melamine resin. A resin (melamine resin or a co-condensation resin of a melamine resin and another resin) is used. Melamine resin is a high molecular weight synthetic resin that is obtained by the addition condensation reaction of melamine and aldehydes (mainly formaldehyde), and the melamine molecule is bridged by this reaction, and finally has a three-dimensional structure. It is a colorless, transparent and hard resin that is excellent in heat resistance and electrical characteristics (especially arc resistance), and is free of coloration, and has a higher hardness than urea resin, as well as water resistance, chemical resistance, heat resistance, and flame resistance. It also has excellent characteristics.

In the present invention, calcium-based ceramics carrying an antibacterial metal is added to, mixed in with, and contained in the amino resin. As the antibacterial metal, one or more selected from silver, copper and zinc is used, but preferably at least silver is contained, and one or more selected from copper and zinc is contained in this silver. A mixture containing two kinds is used, and particularly preferably silver and zinc are used in combination. These metals have not only antibacterial properties but also antifungal properties and deodorant properties. In the present specification, "antibacterial property" means antifungal properties and deodorant properties in addition to antibacterial properties themselves. Used in.

Next, the antibacterial agent used in the present invention, that is, the calcium-based ceramics carrying an antibacterial metal, has the above-mentioned antibacterial metal in the form of its salt, which is used as calcium phosphate [Ca ₃ (PO ₄ ) ₂ , Ca ₂ P ₂ O _7, etc.], calcium carbonate (CaCO ₃ ), calcium silicate (Ca
O / SiO ₂ = 1 to 3), and one or more calcium compounds selected from hydroxyapatite may be supported on the calcium compound, followed by firing.

As the calcium compound in the present invention, one or more calcium compounds selected from calcium phosphate, calcium carbonate, calcium silicate and hydroxyapatite are used, but tricalcium phosphate or hydroxyapatite is particularly preferable. (= Hydroxyapatite) or those containing these are used. Of these, hydroxyapatite is the main component of bones, teeth, etc., it is weakly alkaline (pH = 7-9) and adsorbs proteins and lipids well. It also has a good affinity with biological components, and it also has an ion exchange capacity. From the point that it has,
It is particularly effective as a carrier for antibacterial metals.

Hydroxyapatite contains Ca ₁₀ (PO
₄ ) ₆ (OH) ₂ [= Ca ₅ (PO ₄ ) ₃ (OH)], but with a stoichiometric Ca / P molar ratio of 10
In addition to that of / 6 (= 5/3), the Ca / P molar ratio is 1.
If it is within the range of 4 to 1.8, it is effectively used as a carrier for antibacterial metal in the present invention. Especially in the case of synthetic hydroxyapatite, the molar ratio is exactly 10
In order to obtain / 6, there are certain difficulties in the raw material composition, production conditions, etc., but in the present invention, if the molar ratio is within the above range, it can be used, which is also advantageous. .

As described above, the antibacterial agent is produced by supporting a metal having antibacterial properties against one or more kinds of calcium compounds in the form of its salt, and then calcining it to obtain a ceramic. In the case of tricalcium and hydroxyapatite, because of the above-mentioned excellent properties, they can be effectively used as the antibacterial agent of the present invention without firing, that is, without being made into ceramics. And in this case also in addition to the single composition of tricalcium phosphate and hydroxyapatite, a mixed composition,
For example, whitlockite [Ca:
₃ (PO ₄ ) ₂ ], calcium diphosphate (Ca ₂ P ₂ O ₇ )
And hydroxyapatite can be applied as a mixed composition.

Next, as a method for supporting an antibacterial metal on a calcium compound, for example, an antibacterial metal is made into an aqueous solution of its salt (nitrate, acetate, etc.), and one of the above calcium compounds or Charge and mix two or more kinds of powders for ion exchange adsorption and immobilization, and make an antibacterial metal into an aqueous solution or suspension of its salt, and add one or more kinds of calcium compound powders to it. It can be carried out in such a mode that the metal salt is mixed and impregnated and adsorbed with the metal salt, and then immobilized. In this respect, in particular, in the case of hydroxyapatite, in addition to the above-mentioned embodiments, the salt of the antibacterial metal can be coexisted and supported at the time of its synthesis. This synthesis method includes dry method, hydrothermal method, wet method,
There are mechanochemical method, alkoxide method, etc., and coexistence and loading of the salt of the antibacterial metal can be applied by any of these synthetic methods.

In the case of this embodiment, for example, the antibacterial metal is in the form of a salt such as nitrate or acetate, and this is used in an aqueous solution of calcium salt such as calcium chloride and phosphate such as disodium phosphate. It can be supported by coexisting. In the case of hydroxyapatite, the desired antibacterial effect can be obtained without firing even when the antibacterial metal is supported in any of the above-mentioned modes. However, by further baking this into ceramics, the antibacterial metal is supported more firmly,
It is possible to more effectively prevent the elution and discoloration of the antibacterial metal after mixing and molding into the amino resin, and to eliminate them substantially.

Then, the calcium compound carrying the antibacterial metal is fired in the above-mentioned manner (except when tricalcium phosphate or hydroxyapatite is used without firing), and the firing is used to obtain a ceramic. It is a thing. The firing temperature varies somewhat depending on the type of each calcium compound, but in each case, the firing temperature is preferably about 800 ° C or higher. For example, if you add silver to calcium phosphate and heat it, it will be about 8
The color changes from 00 ° C to white and firmly holds the metal, and hydroxyapatite causes firing shrinkage from about 800 ° C, thereby firmly holding the metal and making it more difficult for metal ions to be eluted. It is because

The inventors of the present invention have previously developed and applied for antibacterial hydroxyapatite in which antibacterial metal ions are supported on hydroxyapatite and a method for producing the same (Japanese Patent Laid-Open No. 2-180270). In the present invention, (1) an antibacterial agent containing antibacterial hydroxyapatite, and (2) an antibacterial agent containing antibacterial hydroxyapatite ceramics obtained by firing the same are amino resins, and in particular, melamine resin. A melamine resin molded article having excellent antibacterial properties can be obtained by mixing the powder and molding it.

Further, as an antibacterial agent, an antibacterial agent containing any one or both of the above (1) antibacterial tricalcium phosphate and antibacterial hydroxyapatite, or (2) an antibacterial phosphoric acid obtained by firing the same. When using an antibacterial agent containing one or both of tricalcium ceramics and antibacterial hydroxyapatite ceramics, it is desirable to add a coupling agent. As a result, when these antibacterial agents are mixed with the resin, the binding property can be enhanced and the antibacterial agent can be present uniformly and firmly. The coupling agent is not particularly limited, but examples thereof include epoxysilane and aminosilane. In this case, the coupling action is C in tricalcium phosphate, hydroxyapatite or their ceramics.
It is due to the component a, and when hydroxyapatite or hydroxyapatite ceramics is used, the "OH group" in the hydroxyapatite or hydroxyapatite ceramics has a further effect.

The amount of the antibacterial metal supported is 50% by weight or less, preferably 0.001 to 30% by weight in the antibacterial agent.
Is used, and more preferably 0.01 to 10% by weight. If the supported amount is 0.001% by weight or more, it can effectively act and be applied as an antibacterial agent, but further 0.0
If it is 1% by weight or more, it is sufficiently effective. On the other hand, the upper limit is 10% by weight, but it is 10% by weight.
It is preferable to use it in the range of up to 10% by weight, and the reason is that if it exceeds 10% by weight, calcium phosphate will become a silver salt, which will be a problem in return.

In the present invention, the above antibacterial agent is added to and mixed with the amino resin powder, and the content is at least 0.03% by weight in the resin powder.
When at least 0.03% by weight or more is mixed and the resin powder is molded in this way, the amino resin molded body is not contaminated by microorganisms and has an effective antibacterial function and antifungal effect on the amino resin molded body. A function and a deodorizing function can be added.

Further, the molded body in the present invention is a decorative board,
It can be applied as a molded product for various laminated plates, tableware, household appliances, various electrical parts, wiring appliances, etc., and can be advantageously applied particularly as a molded product for repeatedly used home appliances. Specific examples thereof include tableware such as cups and plates for homes, school meals, hotels, restaurants, or aircraft, ashtrays and trays, trays, trays, etc.
Examples include spoons and chopsticks. The molded article for firmware referred to in the present specification is meant to include these.

Further, an amino resin molding powder according to the present invention,
In addition, when a molded product formed from this resin molding powder or an amino resin molded product having a glaze layer, monochromatic colored paper or a decorative print on the surface is used, the amino resin as the main component is reinforced to reinforce it. A material called a "base material" or a "filler" can be added to the composition, which can reinforce the brittleness by itself. Further, a curing agent, a plasticizer, a pigment (coloring agent) and the like can be added as appropriate, whereby desired properties can be imparted.

The "filler (base material)" is a cellulosic material.
S (α-cellulose), charcoal, sulfite pulp,
Organic fillers such as paper, lint and cloth scraps and inorganic fillers such as asbestos, mica and glass fibers are used depending on the use and characteristics of the molded product. Melamine resin has a characteristic that it is highly saturated and can be freely colored, and for decorative applications utilizing this characteristic, a dissolving pulp (rayon pulp) containing high-purity α-cellulose. Is the most widely used. Compared with charcoal and other fillers, this α-cellulosse exhibits not only translucency but also high mechanical strength due to the properties of its fibers.

Examples of the above-mentioned curing agent include inorganic acids, organic acids, acidic salts such as sodium acid sulfate, carboxylic acid esters such as dimethyl oxalate, maleic anhydride and phthalic anhydride. Acid anhydrides, monohaloacetic acid sodium salts and organic halides such as α, α'-dichlorohydrin, amines such as ethylamine hydrochloride and triethanolamine acid, hydrochloric acid, ammonium chloride, ammonium sulfate, etc. Examples thereof include ammonium salts, urea derivatives, diammonium imidosulfonate, urea adducts of salicylates, urea adducts of stearates, urea adducts of heptanoates, triazine derivatives, and N-trimethyltaurine.

As the plasticizer, water, monovalent and polyvalent alcohols, ketones, triphenylphosphine are used.
, Glyceryl phthalate resin, monohydric alcohol ester of fatty acid of dried oil or semi-dried oil, higher alcoholic acid sulfuric acid ester or its mixture with polyhydric alcohol, monocresyl glyceryl ether -Tell, etc. can be used, and the quantitative ratio thereof is in the range of about 0.5 to 2% by weight. Furthermore, examples of the release agent include stearic acid and various metal salts thereof (Zn, Mg, Ca, Al), fatty acids, waxes, and the like, and the quantitative ratio in this case is about 0.1 to 0.5 weight. It is applied in the range of%.

Further, as the colorant (pigment), the following examples can be given for each kind of required color,
These pigments can be added by uniformly adding and mixing one kind or two or more kinds to the resin powder. White: Titanium white, Black: Carbon black, Yellow: Cadmium yellow, Benzidine yellow, Hansa yellow, Orange: Chrome vamilion, Cadmium orange, Red: Permanent red 4R, Lake red C,
Carmin 6B, Watching Red, Rhodamin Ray
Ki, Marun: Bon Marun, Bold-10B, Rouge, Band Senna, Yellow Oker, Cadmium Marun, etc., Blue: Cobalt Bull, Phthalocyanine Bull, Sky Bull, Mineral Violet, etc.

[0038]

EXAMPLES The present invention will be described in more detail based on the following examples, but it goes without saying that the present invention is not limited to these examples. First, in Example 1, a production example of an antibacterial hydroxyapatite-containing ceramic is described, and then a color change test (including: shape change, etc.) and an antibacterial activity test performed on a melamine resin to which the antibacterial hydroxyapatite is added are included as comparative examples. It is described in contrast with 1 to 5. In Example 2, a production example of antibacterial tricalcium phosphate ceramics is described, and a color change test, an antibacterial activity test and the like are performed in the same manner as in Example 1 and are described in comparison with Comparative Examples 1 to 5. .

Example 1 <Production Example of Ceramics Containing Antibacterial Hydroxyapatite> 1.0 kg of hydroxyapatite, 47 g of silver nitrate and 110 g of zinc nitrate in 10 l (10 liters) of distilled water.
Was added, and the mixture was thoroughly stirred, mixed and ion-exchanged, and the obtained product was thoroughly washed with distilled water and then dried.
Next, the dried material was fired at a temperature of 900 ° C., and the obtained fired material was pulverized to obtain a hydroxyapatite-containing ceramic powder carrying silver and zinc, which was used as an antibacterial agent for the examples. The amounts of silver and zinc supported on this powder were 2.9% by weight and 3.2% by weight, respectively (inner number, that is, the same after 100 in the total amount after mixing 100).

On the other hand, each antibacterial agent for Comparative Examples 1 to 5 was produced according to the above Production Example. Ag and Zn are used as the antibacterial metal [the loading ratios (weight%) of both metals Ag and Zn in each of Comparative Examples 1 to 5 are as shown in Table 1], and the carrier is A type zeolite in Comparative Example 1. In Comparative Example 2, the same amount of A-type zeolite and zinc oxide was used, in Comparative Example 3, zinc oxide was used, and in Comparative Examples 4 to 5, amorphous silica was used. In Example 5, Ag and Z
n are used in different quantitative ratios.

Example 2 <Production Example of Antibacterial Tricalcium Phosphate Ceramics> As in Example 1, 1.0 l of tricalcium phosphate, 47 g of silver nitrate and 110 g of zinc nitrate were added to 10 l (10 liters) of distilled water. In addition, after thoroughly stirring and mixing for ion exchange, the obtained product was thoroughly washed with distilled water and then dried. Next, the dried material was fired at a temperature of 1200 ° C., and the obtained fired material was pulverized to obtain a powder of tricalcium phosphate ceramics carrying silver and zinc, which was used as an antibacterial agent for Example 2.

<Discoloration test, antibacterial activity test, etc.> Melamine resin-based commercially available melamine resin powder used in the transparent glaze portion (main component: melamine resin, benzoguanamine resin, manufactured by Nippon Carbide Industry Co., Ltd., trade name " Nika glaze "), the antibacterial hydroxyapatite-containing ceramics obtained in the above production example is mixed in an amount of 2% by weight (inner number, that is, 100 after mixing, the same applies hereinafter), A melamine resin product was produced by coating the melamine-based transparent glaze portion on the already formed melamine resin molded body. The presence or absence of discoloration of this melamine resin product, the presence or absence of shape change as a molded body, etc. are investigated at the time of molding (at the end of molding), at the time of boiling for 15 hours and after one month, and the degree of discoloration is also examined. The force test was performed by the shake flask method. Table 1 shows these results.

[0043]

[Table 1]

The antibacterial activity test was carried out as follows (1) to (7). (1) Using Escherichia coli as a bacterium, 60 ml of a broth (manufactured by DIFCO, nutrient broth, hereinafter referred to as NB), which had been sterilized under high-pressure steam, was inoculated with Escherichia coli, and cultured at 37 ° C. for 18 hours with shaking. (2) 1 mM
(1 mmol) NB aqueous solution was added to phosphate buffer 1 /
1000 NB solution (final concentration 1 mM phosphate buffer, 1/1000 NB). (3) The Escherichia coli solution cultured in (1) was diluted with the solution in (2) to obtain a viable cell count of 2.0 × 10.
⁵ cells / ml was used as the E. coli test solution. (4) A test sample was weighed in a 0.1 g sterilized tube, and the phosphate buffer solution prepared in (2) was added to 2% (% by weight, the same applies hereinafter).
After making a test solution and subjecting it to ultrasonic waves for 5 to 10 minutes, 0.2%, 0.1% with the phosphate buffer prepared in (2).
%, 0.02%, 0.01% ..., and 10-step dilution was performed.

Equal amounts of the E. coli test solution prepared in (3) were added to the diluted solutions of (5) and (4), the lid was closed, the tube was shaken well, and the test solution and the bacterial solution were mixed. (6) 25 test samples
It was shaken at 150 ° C., amplitude 2 cm, horizontal 150 rpm.
As a control, only the bacterial solution was also tested simultaneously. (7) The number of bacteria in the E. coli test solution at the start of the test was determined by the pour plate culture method. Further, 6 hours after the start of shaking, 1 ml of the liquid in each tube was sown on a sterilized dish, and 15 ml of ordinary agar medium (manufactured by Nissui Pharmaceutical Co., Ltd.) which had been sterilized by high pressure steam in advance was added and solidified. This was cultured for 48 hours in a 37 ° C incubator and the number of bacteria was measured.

As is clear from Table 1, in regard to the presence or absence of discoloration, in Example 1, no change was observed at the time of molding, after 15 hours of boiling and after a lapse of days (1 month). On the other hand, in Comparative Examples 1, 2, 4, and 5, the color has already changed during molding. Further, in Comparative Example 3, there is no discoloration after molding, but swelling occurs after 15 hours of boiling (not shown in Table 1, but the same thereafter), which is unsuitable as a molded product. It is shown that.

For the antibacterial test, blank, 2
% (Wt%) added product and control viable cell count, Example 1
Also, Comparative Examples 1 to 5 show the same value. But,
Judging this together with the test results for “presence or absence of discoloration” and “presence or absence of shape change” shown in Table 1, in comparison with Comparative Examples 1 to 5, Example 1 or the present invention has excellent effects. It is clear that Although Escherichia coli was used as a test strain in the above-mentioned antibacterial test, the same excellent antibacterial property was observed in the same experiment using Staphylococcus aureus.

<Examples 3 to 5> In Example 1, a commercially available melamine resin used for the transparent glaze portion of melamine resin (main component: melamine resin, benzoguanamine resin, manufactured by Nippon Carbide Industry Co., Ltd., Product name "Nikagure-
")" Powder was mixed with antibacterial ceramics supporting antibacterial metal ions as an antibacterial agent so as to be 2% by weight. In Examples 3 to 5, the same antibacterial effect was used. Example 1 using the agent and the resin and changing the addition amount to 6.0% by weight, 8.0% by weight and 10.0% by weight.
An antibacterial test by the shake flask method was carried out in the same manner as. Table 2 shows these results.

[0049]

[Table 2]

In Table 2, "after endurance test" means an acid resistance test after immersion in a 4% acetic acid aqueous solution for 24 hours (room temperature), and then an alkali resistance test in a 0.5% Na ₂ CO ₃ aqueous solution for 2 hours. This means after 15 hours of boiling after boiling (that is, the same sample was subjected to an acid resistance test + alkali resistance test + boiling test. This also applies to Table 3).
As is clear from Table 2, when the antibacterial agents were added to the melamine resin in the amounts of 6.0, 8.0 and 10.0% by weight respectively, the sterilization rate was 100% before the durability test and 99 even after 15 hours of boiling. %, Indicating that an excellent antibacterial effect is obtained.

Example 6 In this Example 6, an epoxysilane coupling agent (KBM40) was added to the antibacterial hydroxyapatite-containing ceramic obtained in Example 1.
3, Shin-Etsu Chemical Co., Ltd., trade name) 3% by weight (external number, that is, relative to the ceramics 100) was used, except that the static method was applied as the test method, and the resin and other points used Was subjected to an antibacterial test in the same manner as in Example 1. The test operation was performed as follows. First, the bacterial solution was prepared by suspending Escherichia coli cells in an ordinary agar slant medium (SCDLP agar medium, manufactured by Nissui Pharmaceutical Co., Ltd.) at 35 ° C. overnight in a sterilized 1/1000 concentration ordinary broth.
It was adjusted so that the number of bacteria was about 10 ⁶ per ml.

Next, 0.2 ml of the above-mentioned bacterial solution was inoculated to the sample, and after the polyethylene film was adhered, it was stored at 35 ° C., and the surviving bacteria were washed out on the SCDLP agar medium at the start of storage and 24 hours later. The viable cell count of this washout solution was measured by an agar plate culture method (35 ° C., 1 day) using a cell count measuring medium, and converted into the viable cell count per sample. Further, the same amount of bacteria as that inoculated to the sample was dispensed into a dish, and a polyethylene film was adhered and stored, and the number of viable bacteria was measured and used as a control.

<< Embodiments 7 to 9 >> In Embodiment 7, Embodiment 2
The antibacterial tricalcium phosphate ceramics obtained in 1. was treated with a coupling agent in the same manner as in Example 6, and a sample was prepared in the same manner as in Example 6 to perform an antibacterial test. In Example 8, the antibacterial ceramics obtained in Example 6 was used as the urea resin powder to prepare a sample in the same manner as in Example 6, and the antibacterial test was performed. Further, in Example 9, a sample was prepared by using the antibacterial ceramics obtained in Example 6 in the aniline aldehyde resin powder and in the same manner as in Example 6, and the antibacterial test was performed. Table 3 shows these Examples 6-9.
The results of are described.

As shown in Table 3, it is clear that the use of the coupling agent in mixing with the resin imparts excellent antibacterial properties, and in any of the Examples,
No discoloration or elution of silver and zinc was observed even after one month. Further, the same test was performed using Staphylococcus aureus as the bacterial solution, and in this case, the same effect as in the case of Escherichia coli was obtained. The adjustment of the bacterial solution in this test is
Staphylococcus aureus was cultivated overnight on an ordinary agar slant medium at a temperature of 35 ° C., and the cells of the test strain were suspended in ordinary broth having a sterilized 1/100 concentration so that the number of bacteria per ml was adjusted to about 10 ⁶ . It is a thing.

[0055]

As described above, in the present invention, one or more calcium-based ceramics selected from calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite supporting an antibacterial metal are used as the antibacterial agent. As a result, it is possible to impart effective and excellent antibacterial properties to the molded product of the amine resin. In addition, since the molded product according to the present invention has no discoloration or deformation such as swelling as a molded product and no elution of metal, it can be extremely effectively applied as a form of a wear-molded product or other various molded products that are repeatedly used for washing. You can

When tricalcium phosphate or hydroxyapatite is used as the calcium compound, it is effective without firing because of its excellent properties, and the properties can be further ensured by firing. This tricalcium phosphate or hydroxyapatite is used as a single composition as well as a mixed composition containing other calcium compounds, regardless of whether or not it is fired.

[0057]

[Table 3]

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location C08K 7/18 C08K 7/18 (72) Inventor Akio Takimoto 3-36 Noritake Shincho, Nishi-ku, Nagoya-shi, Aichi Noritake Company Limited (72) Inventor Kenji Sakamoto 3-36 Noritake Shinmachi, Nishi-ku, Nagoya-shi, Aichi Prefecture No. 36 Noritake Company Limited Limited (72) Takashi Kanie 3-chome, Noritake Shin-cho, Nishi-ku, Aichi Prefecture No. 1-36 Noritake Company Limited (72) Inventor Komitsu Oba No. 1-336 Norimtake Shinmachi, Nishi-ku, Nagoya-shi Aichi Prefecture Noritake Company Limited (72) Inventor Kenji Kawamoto Nagoya City, Aichi Prefecture Noritake Campani Limited Limited, 1-33, Noritake Shinmachi, Nishi-ku (72) Inventor Hiroshi Sakurai, 3-11-6 Tsukiji, Chuo-ku, Tokyo (72) Inventor, Akira Inose, Tsukiji, Chuo-ku, Tokyo -11-6 Sangi Co., Ltd. (72) Inventor Kiminori Atsumi 3-11-6 Tsukiji, Chuo-ku, Tokyo Sangi Co., Ltd. (72) Inventor Keijiro Fujita 3-11-6 Tsukiji, Chuo-ku, Tokyo In Sangi

Claims (15)

[Claims] 1. An amino-based resin molding powder, comprising one or more selected from calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite, the resin powder carrying an antibacterial metal as an antibacterial agent. Amino resin molding powder, characterized by being mixed with calcium ceramics. 2. The amino resin molding powder according to claim 1, wherein the antibacterial metal contains at least silver and is one or more metals selected from silver, copper and zinc. 3. A ceramic containing the antibacterial metal-supported calcium-based ceramic containing either or both of antibacterial metal-supported tricalcium phosphate and antibacterial metal-supported hydroxyapatite. The amino resin molding powder according to claim 1 or 2. 4. An antibacterial agent made of ceramics containing either or both of the antibacterial metal-supported tricalcium phosphate and the antibacterial metal-supported hydroxyapatite is treated with a coupling agent. The amino resin molding powder according to claim 3, which is an antibacterial agent. 5. The amino resin molding powder according to claim 1, 2, 3 or 4, wherein the amino resin molding powder is a melamine resin. 6. One or more calcium-based ceramics selected from calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite supporting an antibacterial metal as an antibacterial agent for an amino-based resin molding powder. An amino resin molded product, characterized by being formed by mixing mixed amino resin molding powder. 7. The amino resin molded product according to claim 6, wherein the molded product is a homeware molded product. 8. An amino resin in a glaze layer thinly coated on the surface of an amino resin molded article, an amino resin impregnated in a monochromatic colored paper as the surface layer, or the surface layer thereof. Which is an amino-based resin molded product having an amino-based resin impregnated in a decorative print, which is selected from calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite in which the amino-based resin carries an antibacterial metal. Or a glaze layer on the surface of which contains two or more calcium-based ceramics,
Amino resin molded product with monochromatic colored paper or decorative print. 9. The amino resin molded article according to claim 6, wherein the amino resin of the amino resin molded article is a melamine resin. 10. An antibacterial metal containing at least silver and containing copper and / or zinc is supported on a calcium-based compound selected from calcium phosphate, calcium carbonate, calcium silicate and hydroxyapatite, and the compound is heated to a temperature. After firing at 800 ° C. or higher, it is pulverized to an average particle size of 10 μm or less, and the obtained calcium-based ceramic fine powder and amino resin are contained in the fine powder at least 0.0
A method for producing an amino-based resin molded body, which comprises mixing 3% by weight. 11. The method for producing an amino resin molded article according to claim 10, wherein the amino resin is a melamine resin. 12. An amino resin molding powder, wherein the resin molding powder contains either or both of tricalcium phosphate carrying antibacterial metal and hydroxyapatite carrying antibacterial metal. An amino resin molding powder comprising an antibacterial agent obtained by treating an antibacterial agent with a coupling agent. 13. The amino resin molding powder according to claim 12, wherein the amino resin molding powder is a melamine resin molding powder. 14. A coupling agent for an amino resin powder containing an antibacterial agent containing one or both of tricalcium phosphate supporting an antibacterial metal and hydroxyapatite supporting an antibacterial metal. An amino resin molded product obtained by molding an amino resin molding powder mixed with an antibacterial agent treated in step 1. 15. The amino resin molded article according to claim 14, wherein the amino resin molded article is a melamine resin molded article.