JPH04114038A - Master batch for antibacterial antifungal resin and antibacterial antifungal resin composition - Google Patents

Abstract

PURPOSE:To provide a master batch having high safety, being readily handled, having both antibacterial and antifungal activities and employed for antibacterial and antifungal resins by compounding a silver compound, an organic antifungal agent and a wax as main components, and an antifungal resin composition containing the same. CONSTITUTION:A master batch for antibacterial and antifungal resins comprises a silver compound (e.g. silver sulfate or silver chloride), preferably a silver compound having a melting point higher than the processing temperature of a resin to be kneaded therewith and ground into particles of <=0.5mm, (B) an organic antifungal agent [e.g. 2-(4-thiazolyl)benzimidazole], (C) a wax (e.g. polyethylene wax) and, if necessary, a filler, various stabilizers, a metal inactivating agent, etc. The master batch is compounded with a resin in an amount giving 0.01-10wt.% expressed in terms of silver metal) of A, 0.01-10wt.% of B and 0.01-30wt.% of C to provide an antibacterial and antifungal resin composition.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a masterbatch for resins that compensates for the antibacterial properties lacking in organic antifungal agents, and to antibacterial and antifungal resin compositions. It can provide household goods, building materials, paints, fibers, fishing nets, etc. with excellent antibacterial and antifungal properties.

(Prior Art) Antibacterial and antifungal resin compositions containing silver compounds and the like are known (Japanese Patent Application Laid-open Nos. 46464-1984 and 1130-1999).
No. 51, etc.). These products involve kneading silver compounds and the like directly into the resin. However, when a silver compound is kneaded into a resin, it is necessary to add a large amount in order to obtain sufficient anti-mildew performance, which causes the resin to discolor, resulting in a significant loss of commercial value. Another problem was that silver compounds were difficult to handle as they were.

Furthermore, there is no known organic fungicide that is highly safe and has both the heat resistance and antibacterial properties necessary for resin kneading.

(Problems to be Solved by the Invention) The present invention combines a silver compound that is difficult to handle and has the problem of discoloration with an organic fungicide to create an easy-to-handle masterbatch that is highly safe and has antibacterial properties. - Some have been developed with the aim of providing resin compositions that have anti-mildew properties.

(Means for Solving the Problem) The present inventors have discovered that at resin kneading processing temperatures below the melting point, a silver compound will discolor the resin if added in a small amount that exhibits antibacterial properties. It was discovered that it hardly reacted with organic fungicides. Therefore, a masterbatch is made by mixing a silver compound, an organic antifungal agent, and waxes, and a resin made by kneading an appropriate amount of this has excellent antibacterial and antifungal performance with little discoloration. Based on these findings, the present invention has been completed.

The present invention will be explained below.

The silver compound used in the present invention may be selected from those whose melting point is higher than the processing temperature of the kneading resin. When a silver compound is kneaded into a resin at a processing temperature higher than the melting point, the silver compound reacts with the resin and additives in the resin, significantly impairing antibacterial properties and causing significant discoloration of the resin. Therefore, for low-density polyethylene whose processing temperature is about 170°C, for example, silver nitrate (melting point 212°C), silver sulfate (melting point 652°C
) and silver chloride (melting point 455°C), etc., but mixing silver nitrate (melting point 212°C) into polypropylene whose processing temperature is about 220°C should be avoided. Further, it is preferable that the silver compound is crushed into particles of 0.5 mm or less and kneaded into the resin.

The organic fungicide used in the present invention includes phenol ether derivatives such as 1040'-oxybisphenoxaarsine,
N-haloalkylthio compounds such as cyclofluanid,
Imitazole derivatives such as 2-(4-thiazolyl)hense imitazole (abbreviated as TBZ), sulfone derivatives such as 2,3,5,6-titrachloro-4-(methylsulfonyl)pyridine, and quaternary derivatives such as cecylsimethylethylammonium bromide. Examples include grade ammonium salts,
It is not limited to these.

The waxes used in the present invention include plant-based natural waxes (carnauba wax, cantaloupe wax, rice wax, water vein, jojoba oil, etc.), animal-based natural waxes (honey wax, lanolin wax, spermatozoa), and mineral waxes. Natural waxes (montan wax, osikelite, ceresin, etc.), petroleum waxes (paraffin wax, microcrystazone wax, petrolactam, etc.), synthetic hydrocarbon waxes (polyethylene wax, polypropylene wax, Fischer-Tropsch wax, etc.), modified waxes (montan wax, etc.) Metallic stone #7 derived from fatty acids having 12 to 30 carbon atoms; (
Calcium stearate, zinc stearate, etc.), antistatic agents (glycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester) esters, etc.), hydrogenated castor oil, hydrogenated castor oil derivatives, chlorinated hydrocarbons, and blended waxes containing the above waxes as main components9. At least one kind, at least one kind of organic fungicide, and at least one kind of wax are added and mixed, and a part or all of the wax is melted by heat generated by mixing and/or heating. As a result, a master hatch of a silver compound and an organic fungicide using the wax as a binder can be obtained. Mixing is usually carried out in air at atmospheric pressure, but mixing may also be carried out under different pressures or in an inert gas.

In addition, the shape of the masterbatch is granular, powder, granular,
It can be made into crushed pieces, etc., and can be selected depending on the purpose. There is no particular restriction on the ratio of the silver compound or organic fungicide to the total weight of the master hatch. There is no particular restriction on the ratio of the wax to the total weight of the masterbatch. Additionally, useful additives may be added to the masterbatch, such as fillers, titanium oxide, zinc oxide,
Carbon black, pigments, UV absorbers (benzotriazoles, benzophenones, aryl esters, oxanilides, cyanoacrylates, formamidines, nickel compounds, etc.), UV stabilizers (hindered amine compounds, etc.), antioxidants (phenol-based, hindered phenol-based, sulfur-based compounds, etc.), processing stabilizers (phosphorus-based compounds, etc.), metal deactivators (hydrazine-based compounds, etc.), and the like.

The resin used in the present invention includes thermoplastic resin, thermosetting resin,
Crosslinked rubbers, synthetic fibers, semi-synthetic fibers, and recycled fibers can be used alone or in combination, including polyethylene, polypropylene, ABstif resin, nylon, polyamide, polyester, vinyl chloride, polyvinylidene chloride, polystyrene, polyacetal, and polyvinyl alcohol. ,
Polycarbonate, vinylidene, Eva resin, acrylic resin, fluororesin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, urethane resin, polyurethane elastomer, polyester elastomer, rayon, cupro, acetate, natural rubber and synthetic rubber You can choose from the group consisting of: In addition, additives that are useful when added to these resins, such as fillers,
It may also contain plasticizers, stabilizers, lubricants, antioxidants, ultraviolet absorbers, antistatic agents, metal deactivators, pigments, and the like.

The antibacterial and antifungal resin composition according to the present invention can be classified into molded products (films, sheets, pipes, molded products, etc.)
It can be applied to foams, paints, adhesives, resin coatings, fibers, composite materials, etc., and its shape and size are not particularly limited. In the case of fibers, they can be used in fabrics, paper, nonwoven fabrics, etc. in combination with fibers of different types that are not made of antibacterial and antifungal resin compositions. Furthermore, if the proportion of the silver compound to the total weight of the composition is less than 0.001% by weight, antibacterial properties are not observed, and if it exceeds 10% by weight, the properties of the resin will be significantly impaired, so it cannot be used.
More preferably, the range is 0.005 to 5% by weight, and the proportion of the organic fungicide to the total weight of the composition is 0.005 to 5% by weight.
If it is less than 0.01% by weight, there is almost no anti-mold property, and if it exceeds 5% by weight, there will be problems such as blooming.The content is preferably in the range of 0.05 to 1% by weight, based on the total weight of the wax composition. The proportion is preferably 0.001% to 30% by weight.

Furthermore, the antibacterial and antifungal resin composition according to the present invention can be obtained by kneading the masterbatch according to the present invention into a resin using, for example, an extruder.

(Effects of the Invention) The master hatch made of the silver compound, organic fungicide, and wax of the present invention is coated with wax, so even if it is touched directly with the hand, it will not cause skin irritation. It is easy to handle, has no dispersion spots when kneaded into a resin, and can provide a uniform antibacterial and antifungal resin composition. In addition, the antibacterial and antifungal resin composition using the masterbatch of the present invention can be applied to a wide range of everyday household items (e.g., textile products, kitchen utensils, sanitary products, interior materials for buildings, etc.) with antibacterial and antifungal properties. can be granted,
This is a great contribution.

(Example) Next, the present invention will be explained in more detail with reference to Examples. As an organic fungicide, TBZ (imidazole derivative), which is highly safe and has excellent heat resistance and is most commonly used for kneading into plastics, will be explained as an example.

Example 1 (Preparation of masterbatch) 10 g of silver sulfate, TBZ (San-Ai Oil Co., Ltd., Sun-Aisol 10) soaked in a mortar and filtered (100 mesh)
0) 10(l) and 'Polyethylene wax (Hoechst Japan, PE520) 180Q were placed in a high speed mixer (Mizosei Kagaku) and stirred at 5000 revolutions per minute to obtain a granular masterbatch with a diameter of 1 to 5 mm.

Reference Example 1 (Preparation of a masterbatch consisting of a silver compound and waxes) Soaked in a mortar and poured into a sieve (100 mesh), 209 silver sulfate and polyethylene wax (Hoechst Japan, PE520) 180 () were mixed. Place in a high-speed mixer (Mizosei Kagaku) and stir at 5,000 revolutions per minute until 1 to 5a+.
A masterbatch consisting of a granular silver compound of sφ and waxes was obtained.

Reference Example 2 (Preparation of masterbatch consisting of TBZ and waxes) TBZ (San-Ai Sekiyu, Sun-IC/1,1100) 2
0 o and polyethylene wax (Hoechst Japan PE
520) 1goQ was placed in a high-speed mixer (manufactured by Mizosei Kagaku) and stirred at about 5000 revolutions per minute to obtain granular master hatches with a diameter of 1 to 5 mm.

Example 2 (Silver ion elution test of Master Hatchi) The Master Hatchi obtained in Example 1 and Reference Example 1 were soaked in a mortar, and 0.1 g of the master hatch was placed in 50 ml of pure water and stirred with a stirrer for 30 minutes. Afterwards, the concentration of silver ions in the P solution was measured using an ion meter (Denki Kagaku Keiki 10L).
Table 1 shows the results measured with the 30 type. This measurement result shows that silver sulfate is well coated with wax.

using polypropylene resin (Mitsui Petrochemical J-700)
P) to obtain 60×49×2, 5o+o+ test heaths (test piece symbols are . . . , B, and C, respectively). First jtJJ discoloration of this test specimen and light fastness test using a fade-o-meter (40 hours at 63℃)
The results are shown in Table 2.

A (Example 1) No discoloration No change B (Reference Example 1) No discoloration No change C (Consideration Example 2)
No discoloration No change Example 1195 Reference example 1203 Example 3 (Masterbatch mixing test) Silver sulfate and/or TBZ was 0.1% by weight for the masterbatch obtained in Example 1, Reference Example 1, and Reference Example 2. (0.07% by weight in terms of silver ions) using an injection molding machine (
Temperature setting: 220°C) Example 4 (Antibacterial test) A bag was made by heat-sealing polyethylene film (Steel Chemical, Frozen M) so that the 60 x 49 x 2.5 dragon test piece obtained in Example 3 would fit inside. .

This bag contains Frank's polypropylene resin test piece, which is about the size of a spinner.
An antibacterial property test was conducted using IFQ 3060) using a pressurized contact method. After dropping 11 drops of the bacterial solution over a 0.3 m area into the polyethylene bag containing these test pieces, the bacterial solution was spread over both sides of the test piece, and then the air inside the film was evacuated to make it airtight.

After that, the bag was pressurized with a weight and placed in a separate container, and after 24 hours, the bacteria in the bag was washed out with phosphate buffer (10 mN).
For 1rrl of this washout, the number of surviving bacteria was measured by pour plate culture using 5CDLP agar medium. As a result (Table 3), a test piece in which only TBZ was kneaded<
Except for C>, remarkable antibacterial effects were observed.

(Initial number of bacteria added) Blank A (Example 1) B (Reference Example I C (Example 2 6.0xlO'1.7xlO' 〈10 )〈10 > 9.0x104 3 1x10' 2 8x10' 〈10 〈10 A 2.5x10' pre-sterilized potato textulose agar medium was placed in a Petri dish and allowed to solidify.Example 3 was placed on top of the agar medium.
The 60x49x2, 5a+m test piece obtained in step 1 was placed. Five platinum loops of Aspergillus niger (IFO4414) separately cultured in 10 mN of a 5% dioctyl sodium sulfosuccinate aqueous solution are taken, and the spores are separated by centrifugation. Transfer the spores to 10 m of G P L P medium.
The bacterial solution placed in J7 was sprayed onto a test piece in a Petri dish, and cultured in a futurator at 25°C for 17 days.

From the results (Table 4), it was found that silver sulfate and T
The product (A) in which BZ was mixed was found to have remarkable mold resistance, perhaps due to a synergistic effect.

Blank A that covers 50-100% of the mycelium or surface (
Example 1) Microscope without mycelial growth B (Reference Example 1) Example 5 with mycelia covering 25-50% of the surface (Mold resistance test)

Claims (1)

[Scope of Claims] 1. A masterbatch for antibacterial and antifungal resin which mainly comprises at least one silver compound, at least one organic antifungal agent, and at least one wax. 2. An antibacterial and antifungal resin composition comprising the masterbatch according to claim 1.