JP2969472B2 - Manufacturing method of antibacterial material and antibacterial material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention is not a method of subjecting a molded article made of various polymers to metal ion treatment after molding, but in order to impart antibacterial properties to the entire molded article. Easily mixed with various polymers,
The present invention relates to a method for producing a molded antibacterial material and a method for producing a molded antibacterial material by mixing a molded antibacterial crosslinked spherical copolymer with the various polymers.

(Prior Art) It is known that copper ions and silver ions exhibit excellent antibacterial properties. These metal ions are used in various fields as fungicides or disinfectants in the form of salts. On the other hand, research is also being conducted to obtain antibacterial materials by bonding metal ions to polymers. For example, Japanese Patent Publication No. 60-45643 is such. This is a proposal to form a polymer obtained by polymerizing a sulfonic acid group-containing alkyl acrylate and then treat it with an aqueous silver nitrate solution to bind silver ions. However, when used as a bactericide or disinfectant in the form of a salt, it can be present only in the form of a solution, so that its use is currently limited. Also, Tokiko Sho 60-
In 45643, etc., after the molded article is formed, metal ions are bound only after a metal solution treatment, so the molded article has no antibacterial properties, and the antibacterial properties of the surface also decrease due to falling off. There was a problem of inviting.

Also, when the antibacterial material treated with metal ions is used for further forming, there is a problem that metal ions are dropped off.

As an improvement measure, an antibacterial material may be mixed into the entire molded body, instead of a method of treating the molded body with metal ions to impart antibacterial properties. Therefore, there is a need for an antibacterial material which is uniformly mixed with various polymers and has strong metal ion binding.

(Problems to be Solved by the Invention) The problem to be solved is that the antibacterial material is easily mixed with various polymers, is easy to mold, and various polymers which give antibacterial properties to the whole molded article only by mixing and molding. The aim is to develop an antibacterial material that is highly compatible with.

(Means for Solving the Problems) In the present invention, acrylic (methacrylic acid) ester-based crosslinkable ultrafine particles are used as a means for increasing compatibility with various polymers. The crosslinkable ultrafine particles have good mixing properties with other resins and are easy to mold.

Of course, metal ions having antibacterial properties are ionic-bonded to the surface of the crosslinkable ultrafine particles, and as a result, the crosslinkable ultrafine particles have a strong antibacterial effect on the main body and a molded product obtained by mixing the same. .

 The details of the present invention are described below.

The antibacterial base of the present invention is a crosslinked acrylate-based ultrafine particle. In the present invention, the size of the primary particles of the ultrafine particles, which can be well compatible with other various resins by forming the crosslinked ultrafine particles, is suitably about 600 to 2000 mm.

In the present invention, the ultrafine particles are obtained by emulsion polymerization of an acrylate (methacrylate) and a diacrylate (dimethacrylate). An important point in the present invention is that a radically polymerizable emulsifier containing a sulfonic acid group is used as an emulsifier for the emulsion polymerization of the acrylic ester (methacrylic ester) and the diacrylic ester (dimethacrylic ester). . By using a radical polymerizable emulsifier, a sulfonic acid group can be covalently bonded only to the surface of the crosslinked ultrafine particles. By bringing the emulsion obtained by this method into contact with an aqueous solution of copper or silver, it is possible to obtain an antimicrobial material comprising the crosslinkable ultrafine particles of the present invention having copper or silver ions ion-bonded to the surface.

 This will be described more specifically.

The acrylic resin used as the base of the ultrafine particles used in the present invention is a copolymer of an acrylic ester and a methacrylic ester, a di- or triacrylic ester as a crosslinking agent and a di- or trimethacrylic ester and a monomer copolymerizable therewith. Combine.

Examples of diacrylic esters and methacrylic esters include various acrylic esters and methacrylic esters of aliphatic alcohols such as methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate, ethyl methacrylate, octyl acrylate and octyl methacrylate.

Acrylic and methacrylic esters of alicyclic alcohols such as cyclohexyl acrylate, cyclohexyl methacrylate, cyclohexylmethyl acrylate, and cyclohexylmethyl methacrylate. Further, aromatic acrylic esters and methacrylic esters such as phenyl methacrylate, phenyl acrylate, benzyl acrylate and benzyl methacrylate. Further, those containing hydroxyl groups such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, and acrylic esters and methacryl esters containing halogens such as 4-chlorophenyl methacrylate and 4-bromophenyl acrylate can also be mentioned. . Of course, it is not limited to these.

Next, a di- or triacrylic ester of a crosslinking component or
Examples of di- or trimethacrylic esters include ethylene glycol dimethacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate,
Propylene glycol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
Bifunctional diacrylic esters such as polyethylene glycol diacrylate, 1,3-dimethacryloxy-2-propanol, 1,3-diacryloxy-2-propanol,
In addition to dimethacrylic esters, trifunctional acrylic esters and methacrylic esters such as glycerin triacrylate, trimethacrylate and trimethylolpropane triacrylate and trimethacrylate can be used, but the present invention is not limited thereto. is not.

In addition to the main components of these monofunctional and polyfunctional acrylic esters or methacrylic esters, the fine particles of the present invention can use a monomer copolymerizable therewith as the third component. The third component has a meaning that can be adjusted according to the purpose in order to increase the compatibility when the fine particles are mixed with another resin later. Examples of the third component include styrene, divinylbenzene, diallyl phthalate, triacryl cyanurate, vinyl chloride, vinyl acetate, acrylonitrile, α-methylstyrene, butadiene and the like depending on the purpose.

In the present invention, the acrylate or methacrylate is 50 to 98 parts by weight, and the di- or triacrylate or methacrylate as a crosslinking component is 2 to 30 parts by weight per 100 parts by weight of the crosslinked particle matrix. The third component copolymerizable therewith is preferably used in an amount of 1 to 50 parts by weight.

Next, these monomer mixtures are emulsion-polymerized into ultrafine particles. In the present invention, the emulsion is superfinely formed by emulsion polymerization using a radically polymerizable emulsifier containing a sulfonic acid group as an emulsifier. The point has the greatest feature.

For example, having the structure of the following Chemical Formula 1, n ≧ 6, X is H or CH ₃ , Y is H or a compound having a radically polymerizable acryl or methacryl group with a sulfon group of Na, K, NH ₄ , or a compound of the formula 2 in which an allyl group and a sulfonic group are shared. A compound, wherein R represents an alkyl group, a phenyl group, or a benzyl group, and Y is H or Na, K, NH ₄ . Furthermore, a compound having a radical polymerizable double bond and a sulfonic acid group, such as a compound obtained by adding ethylene oxide or propylene oxide to nonylphenol having an allyl group and sulfated, and having an effective emulsifier as an emulsifier is used. Can be

In the present invention, an acrylic emulsion containing a sulfonic acid group by a chemical bond formed as described above is added to a metal aqueous solution of copper or silver ions to precipitate a polymer from the emulsion and simultaneously to polymerize these metal ions. It is possible to combine them. The aqueous metal solution is not particularly limited, but an aqueous solution of copper sulfate, copper chloride, copper nitrate, silver chloride, silver nitrate or the like is frequently used. The precipitated crosslinked acrylic resin is dried well after washing with water. In the present invention, the content of metal ions such as copper or silver ions in the ultrafine particles of the present invention containing copper or silver ions, the cross-linked copolymer 10
The amount between 0.001 g and 10 g per 0 g is preferably used. Below this, when mixed with other resins, the antibacterial property of the molded article is poor, and when it is above this range, the hydrophilicity of the resin increases, and it may not be possible to impart antibacterial properties to the molded article for a long time. It is.

The acrylic ultrafine particles of the present invention containing metal ions in this range exhibit favorable antibacterial properties themselves, but the feature of the present invention utilizes the fact that these fine particles are extremely small and have good compatibility with other resins. Mixed with other resin and molded,
The point is that antibacterial properties can be imparted to these molded articles. The other resin described above, for example, acrylic resin, vinyl chloride resin, styrene resin, various polyolefin resins, epoxy resin, polycarbonate resin, melamine resin, urea resin, urethane resin, fluorine resin, polyester resin,
Other resins can be mentioned. In the present invention, it is possible to mix 3 to 80 parts by weight of acrylic ultrafine particles containing the above-mentioned content of metal ions and 20 to 97 parts by weight of the above-mentioned other resins to be used as a preferable antibacterial material. .

Forming method, after mixing both well, it is possible to form into a thread, film, plate, sheet, and other various shapes using a roll press or the like, further using an extruder, a calendar, or the like. .

As described above, the antibacterial material according to the present invention converts the crosslinkable acrylic resin into ultrafine particles, binds copper and silver ions through the sulfonic acid groups chemically bonded to the surface thereof, and converts this to other general By mixing with a resin and molding, the molded article can be directly used as an antibacterial material, and is highly effective.

(Example) First Example 6 g of an emulsifier having a nonylphenol-based sulfonic acid group whose radically polymerizable functional group is an allyl group (manufactured by Daiichi Kogyo Chemical Co., Ltd., Aqualon HS-10) was dissolved in 300 g of distilled water. To this, 160 g of an acrylate and 40 g of diethylene glycol dimethacrylate were added. to this,
After adding 0.4 g of ammonium persulfate to replace the inside of the system with N _2, polymerization was carried out with good stirring. The polymerization was carried out at 60 ° C. for 4 hours and then at 80 ° C. for 2 hours. This resulted in a good emulsion.

After this emulsion was poured into a large amount of a 10% aqueous solution of copper sulfate, the precipitate was filtered and washed repeatedly with water to obtain a crosslinked copolymer having copper ions on the particle surface. According to atomic absorption analysis, the content of Cu was 0.08 g per 100 g of the crosslinked resin. 10 g of this cross-linked resin is replaced with a commercially available PMMA resin
The mixture was blended with 90 g and press-molded to prepare a transparent test piece having a thickness of about 1 mm. An antibacterial test was performed using this test piece.

The above test piece (100mm disc) and normal PMMA100
Using a 1 mm thick disc, bacteria (Escherichia
coli (Staphylococcus aureus) and mold (Aspergill)
us niger). 3 for bacteria
A culture solution cultured at 5 ° C. for 24 hours is added to an agar medium for measurement, and a disc is placed thereon. After culturing at 35 ° C. for 24 hours and mold at 25 ° C. for 7 days, spores are added to a 0.05% polysorbate aqueous solution for about 10 hours. after 5 days of incubation at 25 ° C. Place the disk on it what liberated so that ⁶ to 10 ⁷ / ml were added to the measurement agar pressurized glucose peptone medium, the presence or absence of inhibition zone formed around the disk As a result of observation, a band was formed around the disk according to the present invention.
No inhibition band was formed around PMMA, confirming the excellent effect of the antibacterial material according to the present invention.

Second Example 4.2 g of a reactive emulsifier having a structure of the formula 1 containing a —SO ₃ Na group in which a functional group is a methacryl group and 250 g of distilled water
Dissolved in, this after the addition of methyl methacrylate 100 g, 2-hydroxyethyl methacrylate 20g, trimethylolpropane trimethacrylate 30g, and styrene 20g, potassium persulfate 0.3g addition, by performing N ₂ substitutions, substantially before the implementation Emulsion polymerization was carried out according to the example to obtain a good emulsion.

This emulsion was placed in a large amount of a 10% silver nitrate aqueous solution and stirred. The precipitate was filtered and washed with water to obtain a crosslinked copolymer retaining silver ions on the particle surface. According to atomic absorption analysis, the content of Ag was 0.12 g per 100 g of the crosslinked resin.

10 g of this crosslinked resin was mixed with 90 g of a commercially available polyester resin and 90 g of a polyvinyl chloride resin, respectively, and press-molded to obtain a transparent test piece having a thickness of about 1 mm. An antibacterial test was performed using this test piece.

When an antibacterial effect test was conducted in the same manner as in the first embodiment, it was confirmed that the antibacterial effect was superior to or superior to that of the first embodiment.

(Effects of the Invention) (a) In the present invention, since a radically polymerizable emulsifier containing a sulfonic acid group is used as an emulsifier for the emulsion polymerization of an acrylate ester and a diacrylate ester, sulfone is applied only to the surface of the crosslinked ultrafine particles. An acid group can be covalently bonded, and the resulting emulsion is brought into contact with an aqueous solution of copper or silver to ion-bond copper or silver ions to the surface, thereby obtaining an antibacterial material having an excellent antibacterial effect.

(B) The antibacterial agent of the present invention and a molding material using the same have excellent antibacterial effects, as well as easiness in the production method and
It can be said that it has compatibility with a wide variety of application materials. In addition to the medical field, it is effective for use in various fields such as textiles, paints, home appliances, fisheries, agriculture, building materials, architecture, eating and drinking, painting, and papermaking.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 61/00 A01N 61/00 D C08F 2/26 C08F 2/26 220/12 220/12

Claims (3)

(57) [Claims] 1. 50 to 98 parts by weight of an acrylate or methacrylate, 2 to 30 parts by weight of a di- or tri-acrylate or di- or tri-methacrylate as a crosslinking agent, and copolymerizable therewith In emulsion-polymerizing 1 to 50 parts by weight of a monomer, polymerization is carried out using a radical polymerizable emulsifier having a sulfonic acid group as an emulsifier, and the obtained cross-linked copolymer emulsion contains copper ions or silver ions. A method for producing an antibacterial material, wherein copper ions or silver ions are contained on the surface of the crosslinked spherical copolymer in an amount of 0.001 to 10 g per 100 g of the crosslinked spherical copolymer. 2. 50 to 98 parts by weight of an acrylate or methacrylate, 2 to 30 parts by weight of a di- or tri-acrylate or di- or tri-methacrylate as a crosslinking agent, and copolymerizable therewith. In order to emulsion polymerize 1 to 50 parts by weight of the monomer, a radical polymerizable emulsifier having a sulfonic acid group is used as an emulsifier,
The crosslinked copolymer emulsion obtained by polymerization is precipitated with an aqueous solution containing copper ions or silver ions, and copper ions or silver ions are applied to the surface of the crosslinked spherical copolymer at a rate of 0.001 to 1001 g per 100 g of the crosslinked spherical copolymer. Antibacterial material made to contain 10g 3 to 80 parts by weight of said crosslinked spherical antibacterial material, and acrylic resin, vinyl chloride resin, styrene resin, polyolefin resin, polycarbonate resin, melamine resin, urea resin, urethane resin, fluororesin, epoxy resin, polyester Resin, mixed with 20 to 97 parts by weight of resin selected from other resins, plate shape, thread shape, particle shape,
3. The antibacterial material according to claim 2, which is formed into a sheet, a film, or the like.