JPH0726058A - Mite-proof and mold-proof resin molding - Google Patents

Abstract

PURPOSE:To provide a mite-proof and mold-proof molding which is excellent in mite-proofing, mold-proofing and antibacterial effects, has good persistence of the effects, is substantially freed from discoloration, etc., does not suffer from especially impaired resin transparency, and can give a container the contents of which can be distinguished from the outside. CONSTITUTION:The molding is made by molding a composition formed by adding 0.01-10 pts.wt. mixture or reaction product of a monohalogenated xylenol with a dihalogenated pyridazine to 100 pts.wt. thermoplastic resin.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin molded product such as a clothing case, which can prevent ticks, molds and the like from adhering and generating not only on the molded product itself but also on the contained product. The present invention relates to a resin molded product having anti-mite and anti-mold properties.

[0002]

2. Description of the Related Art Generally, plastic itself has excellent resistance to mites and molds, but it does not have a repellent action against them, and in cases such as costumes, mites and molds are not The use of insect repellents was essential in order to enter the container and damage its contents. However, this insect repellent has problems that it causes odor and coloring on the costume, requires replenishment, and often forgets to put it in.

[0003] Plastics, which are themselves used as kitchen utensils or water accessories, tend to become slimy or dark due to mold.

In order to prevent these, it has been proposed to add an antibacterial agent consisting of an organometallic compound containing copper, tin or the like to the resin, but these are not sufficiently antibacterial, durable and heat resistant. Recently, a method of adding zeolite holding a metal having a bactericidal action has been proposed (JP-A-3-181538).

However, the method of holding the above-mentioned antibacterial agent in zeolite has the drawbacks that the effect is short-lasting, coloring is further impaired, especially the transparency of the resin is impaired, and a container in which the contents can be seen cannot be made. .

On the other hand, it is known that a dispersion of a monohalogenated xylenol and a dihalogenated pyridazine in a medium or a reaction product has an antifungal effect (Japanese Patent Publication No. 50-66).
No. 00, Japanese Examined Patent Publication No. Sho 56-8004), if these are added to the resin and molded, the resin has an antifungal effect,
It was not known that the resin itself could be given a mites repellent effect.

[0007]

DISCLOSURE OF THE INVENTION The present invention has solved the above-mentioned problems, and an object of the present invention is to be a non-eluting type, which has a long-lasting effect, and has almost no coloring or the like. It is to provide a resin molded product that can identify a contained object from the outside without damaging it.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that when a mixture of monohalogenated xylenols and pyridazines or a reaction product of both is kneaded into a resin. It was found that the resin is provided with a repellent action against mites and fungi, and the transparency of the resin is hardly impaired.

The present invention has been made on the basis of such findings. The present invention is based on 100 parts by weight of a thermoplastic resin, and a mixture of monohalogenated xylenols and dihalogenated pyridazines or a reaction product of both of them is added in an amount of 0.01 to It is an anti-mite and anti-mold resin molded product, which is formed by adding 10 parts by weight and molding.

The present invention can be applied to a resin capable of kneading an organic substance such as monohalogenated xylenols and pyridazines, that is, a thermoplastic resin having fluidity by heat. For example, polyethylene, polypropylene, polyvinyl chloride. , Polystyrene, polyvinylidene chloride, fluororesin, polymethylmethacrylate, polyamide, polyester, polycarbonate, polyphenylene oxide and the like are preferable.

The monohalogenated xylenols are xylenol compounds having an aryl group substituted with one halogen atom, and various isomers can be used, but especially 4-chloro-3,5 -Xylenol, 4
-Bromo-3,5-xylenol, 4-fluoro-3,5-xylenol and the like are preferable. On the other hand, pyridazines have two hydrogen atoms in the pyridazine ring replaced with halogen atoms.
Other hydrogen may be substituted with a hydroxy group, an alkyl group or the like, and particularly 3,6-dichloropyridazine,
3,6-dibromopyridazine, 3,4-dichloro-6-methylpyridazine-1-oxide and the like are preferable.

The monohalogenated xylenols and the dihalogenated pyridazines may be used as they are by mixing one or more kinds of the above-mentioned compounds in a medium such as water or a surfactant, if necessary. Well, or by mixing, both react at room temperature, but this reaction product can be used separately.

To the monohalogenated xylenols and pyridazines, a trialkyltin hydroxide compound composed of a lower alkyl group such as methyl, ethyl, propyl, isobutyl, tert-butyl or isobutyl can be added. And, it is possible to enhance the effect of preventing ticks and fungi. For these compounds, see Japanese Patent Publication No.
Details are disclosed in JP-A-0-6600 and JP-B-56-8004, and the compounds disclosed herein can be used as they are in the present invention.

The total amount of the above compounds is 10
0.01 to 10 parts by weight, particularly preferably 0.05 to 2 parts by weight, is added to 0 parts by weight, but if the amount is 0.01 parts by weight or less, this effect cannot be sufficiently exhibited. Addition of more than one part cannot be expected to improve the effect commensurate with the addition amount, which is uneconomical and causes uneven processing.

The above-mentioned compound can be added to the resin by a generally used method, for example, a method in which the above-mentioned compound and resin pellets are premixed, and then kneaded and molded by an extruder. In this case, a desired resin molded product can be relatively easily prepared by preparing a masterbatch having a high concentration of 1 to 20 parts by weight with respect to 100 parts by weight of the resin by the above-mentioned method and mixing this with a new resin and molding. can get.

In addition to the above-mentioned compounds, other additives such as talc, mica and wollast are added to the resin composition of the present invention for the purpose of modifying the properties of the resin. An inorganic filler such as knight, a heat stabilizer, a light stabilizer, a flame retardant, a plasticizer, an antistatic agent, a release agent, a foaming agent, a nucleating agent and the like can be added. The effects of the present invention will be clarified below with reference to examples.

[0017]

【Example】

(Example 1) Preparation of drug 4-chloro-3,5-xylenol (240 g) was dissolved in 10% aqueous sodium hydroxide solution (45 g), and water was added to the solution.
The total amount was 2400 g. 3,6-dichloropyridazine 1
3 g was dissolved in 62 g of polyethylene glycol having a molecular weight of about 400, and water was added to this to make the total amount 1600 g. The two solutions were mixed, stirred at room temperature for 1 hour, allowed to cool in a cold place, the precipitated crystals were filtered, and washed with water to prepare a drug.

Workability test Propylene-ethylene random copolymer [MFR = 23d
g / min, Mitsubishi Polypro 6806J, Mitsubishi Kasei Co., Ltd.]
4 parts by weight, 6 parts by weight and 8 parts by weight of the above-mentioned drug to 100 parts by weight.
Add 5 parts by weight each and add 5 with a 40l super mixer.
Pre-mix for 1 minute, vent type single screw extruder (40mmφ,
L / D = 22) was used, and the mixture was melt mixed at a screw rotation speed of 80 rpm, an extrusion rate of 10 kg / H and a die temperature of 230 ° C., and pelletized. As a result, the products added with 4 parts by weight and 6 parts by weight could be processed smoothly with almost no discharge unevenness. In the case of adding 8 parts by weight, there was some discharge unevenness, but processing was possible.

Anti-dallinity test Using the pellets containing 4 parts by weight of the above-prepared drug as a masterbatch, the drug was prepared in the same manner as described above.
Pellets each containing 2, 0.5, 2.0 parts by weight were prepared, and the pellets were prepared with a 2 ounce injection molding machine [Yamashiro Seiki Co., Ltd.].
Manufactured by the following method at a molding temperature of 230 ° C., 150 × 150 × 2
A plate having a diameter of 30 mm was formed and cut into a circle having a diameter of 30 mm to obtain a test piece. In addition, a blank test piece was prepared by the same method using a pellet to which no drug was added.

In a plastic container having an internal volume of 1.5 l, six petri dishes having a diameter of 30 mm were arranged in the center of the petri dish so as to be in contact with each other, and a total of seven petri dishes were placed. An adhesive sheet was laid around this to prevent invasion of mites from the outside, and a petri dish containing saturated saline was placed in the corner of the container to keep the humidity inside the container at 75%. Next, six test pieces having 0.2 parts by weight of the drug added thereto and three blank test pieces are staggered one by one on six surrounding petri dishes, and mites are attracted to the test pieces. For this purpose, 0.01 g of a feed (a mixture of powdered feed for experimental animals and dry yeast in the same amount) was placed. Dermatophagoides pteronyssinus on the center dish
Approximately 3200 surviving insects of the Tokyo Women's Medical College
Put the pieces into the dish, leave it at a constant temperature of 25 ° C for a day and night, and extract the number of mites that have moved to each dish by the washing method.
Both the number of surviving and the number of dead were counted under a stereoscopic microscope. The repellent rate was calculated from the obtained number of mites by the following formula.

Repelling rate (%) = 100 × (number of transfers to blank test piece−number of transfers to added test piece) / number of transfers to blank test piece

The same method was applied to the test pieces to which 0.5 and 2.0 parts by weight of the drug was added, and the results are also shown in Table 1.

[Table 1]

From these results, it can be seen that the resin to which the above-mentioned chemicals are added has a mites repellent action.

In the test piece to which the above-mentioned chemical agent was added by 2.0% by weight, a slight yellow coloration was recognized, but the transparency was hardly impaired, and 0.2, 0.8% by weight was added. Almost no coloring was observed on the test piece of No. 1, and transparency was retained.

(Example 2) Preparation of test piece Low density polyethylene [MFR = 6.0 dg / min, density = 0.
923, DFD0148, manufactured by Nippon Unicar Co., Ltd.], homopolypropylene [MFR = 12 dg / min, density = 0.9
0, NH060J, manufactured by Nikko Oil Chemical Co., Ltd.], polyethylene terephthalate [softening point 230 to 240 ° C., melting point 259]
~ 263 ° C, Kuraray Co., Ltd.] 100 parts by weight,
Add 2 parts by weight of the drug prepared in Example 1 and add 40 l
Premix for 5 minutes with a super mixer of No. 1, and use a vent type single screw extruder (40 mmφ, L / D = 22), screw rotation speed 70 rpm, extrusion rate 10 kg / H, die temperature 21.
The mixture was melt mixed and pelletized at a temperature of 0 to 220 ° C. Using these pellets as a masterbatch, pellets to which the drug was added by 0.2, 0.4 and 0.8 parts by weight (only 0.4 and 0.8 parts by weight of polyethylene terephthalate) were prepared by the same method as described above. Prepared and used a 2 ounce injection molding machine [made by Yamashiro Seiki Co., Ltd.] at a molding temperature of 23
15 ° C at 0 ° C (260 ° C for polyethylene terephthalate)
A 0 × 150 × 2 mm plate was molded and used as a test piece.
In addition, a blank test piece was prepared by the same method using a pellet to which no drug was added.

Antifungal test The surface of some of the above test pieces was polished with # 280 sandpaper, and various resins were blank non-surface polishing plate, blank surface polishing plate, 0.2 parts by weight. Non-surface polishing plate, 0.2 parts by weight surface polishing plate, 0.4 parts by weight non-surface polishing plate, 0.4 parts by weight surface polishing plate, 0.8 parts by weight non-surface polishing plate, 0.8 parts by weight JIS surface polishing plate as a set, JIS
The antifungal test was carried out by the method specified in Z 2911 "Mold resistance test method".

The bacteria used are Aspergillus niger (Aspe
rgillus niger) FERM S-1, Penicillium citrinum Thom FERM S-5, Rhizopus stolonifer Lind FERM S
-7, Cladospollium (Cladospo
rium cladosporioides de Vrieg) FERM S-8, Chaetomiumu globosum Kunze ex Frie
s) Using FERM S-11, a sample piece was placed on a potato-glucose-agar medium in a petri dish, and 1 g of the mold spore suspension was sprayed evenly on the dish. Culture was performed at a temperature of 28 ° C. and a humidity of 95 to 99%, and the growth state of mycelia was observed. The results were evaluated according to the following evaluation method and are shown in Table 2. No hyphal growth is observed in the sample …………………… 3 Mycelium is growing in the sample less than 1/3 of the sample ………… 2 Mycelium is growing in the sample more than 1/3 of the sample ............ 1

[Table 2]

From these results, it can be seen that the resin molded product to which the agent of the present invention is added has an antifungal effect.

(Example 3) Preparation of test piece To 100 parts by weight of the same homopolypropylene as used in Example 2, 2 parts by weight of the drug prepared in Example 1 were added, and the mixture was mixed with a 40 l supermixer for 5 minutes. Pre-mixing is performed, using a vented single-screw extruder (40 mm ψ, L / D = 22), melt mixing at a screw rotation speed of 70 rpm, an extrusion rate of 10 kg / H, and a die temperature of 210 to 220 ° C., and pelletizing. Thing Using these pellets as a masterbatch, the pellets containing 0.8 parts by weight of the drug were prepared in the same manner as described above, and the pellets were molded using a 2-ounce injection molding machine (manufactured by Yamashiro Seiki Co., Ltd.). Temperature 230
At 150 ℃, form a plate of 150 × 150 × 2mm,
It cut into the board of * 50mm, and set it as the test piece. On the other hand, a blank test piece was prepared by the same method using a pellet to which no drug was added.

Antibacterial test 20 test bacteria of Escherichia coli IFO 3301 and Staphylococcus aureus IFO 12732 were tested.
The culture solution, which had been shake-cultured overnight at 35 ° C. in a double-diluted normal broth medium, was diluted with a sterilized phosphate buffer solution so that the theoretical number of cells to be added per ml was about 10 ⁵ .

1 ml of the above bacterial solution was dropped on the surface of the test piece,
Store at 25 ° C, and after 6 and 24 hours, wash out the bacteria on the test piece with SCDLP liquid medium (manufactured by Nippon Pharmaceutical Co., Ltd.), and pour plate culture method (35 ° C, 2 days culture) for this liquid using SCDLP liquid medium. The viable cell count was measured by. The results are shown in Table 3.

[Table 3]

From these results, it can be seen that the resin molded product to which the agent of the present invention is added has antibacterial properties.

[0033]

EFFECT OF THE INVENTION The resin molded product of the present invention is excellent in anti-tick, anti-mold and anti-bacterial action, and has a long lasting action.
In addition, there is almost no coloration, and the transparency of the resin is not particularly impaired, and when used as a container, it has excellent effects such as distinguishing the contents from the outside.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location C08K 5/3462 KBJ C08L 101/00 (72) Inventor Takayuki Kawasaki 2-chome Umeda, Kita-ku, Osaka City, Osaka Prefecture 2-25 Nikko Petrochemical Co., Ltd. Osaka Branch

Claims (1)

[Claims] 1. An anti-mitite agent comprising molding by adding 0.01 to 10 parts by weight of a mixture of monohalogenated xylenols and dihalogenated pyridazines or a reaction product thereof to 100 parts by weight of a thermoplastic resin. Mold-proof resin moldings. [0001]