JPH06179824A - Antimildew, easily washable molding - Google Patents

Abstract

PURPOSE:To obtain a composition which does not lose its antimildew effect even when molded at high temperature, is useful as the material of moldings for food and medical uses and can give a molding from which stains can easily be washed off by mixing a thermoplastic resin with a specified copolymer. CONSTITUTION:The composition is obtained by mixing 100 pts.wt. thermoplastic resin with 0.1-10 pts.wt. non-reactive organopolysiloxane/polyoxyalkylene copolymer of formula I (wherein R is H or a monovalent hydrocarbon group; m is 0-10; n is 1-10; x is 2-6; y is 3-10; and A is a monovalent hydrocarbon group) (e.g. a compound of formula II). This composition in not toxic to the human body, can be molded at high temperatures without the heat decomposition or evaporation of the above copolymer as the antimidlew agent, and therefore neither loses an antimildew effect nor worsens working environments. Therefore, it is especially useful as the material of moldings for food and medical uses. Even if such moldings are stained with ink or the like, the stain can easily be washed off from them.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifungal and easily washable molded product and a resin composition for producing the same.

[0002]

2. Description of the Related Art Generally, a thermoplastic resin is not disintegrated by mold itself, but a plasticizer, a stabilizer, an antistatic agent, which is blended for imparting physical properties according to the use,
Since colorants, lubricants, fragrances, etc., and stains attached to the surface of the molded product serve as a nutrient source for mold, mold may be generated in the molded product manufactured from the thermoplastic resin. Particularly in recent years, the environment of high temperature and high humidity has increased, and in such an environment, the generation and reproduction of mold is remarkable, and the molded product itself is decomposed, deteriorated, colored, etc., resulting in deterioration of physical properties and deterioration of aesthetics. Therefore, fungicides such as 2- (4-thiazole) benzimidazole, N- (fluorodichloromethylthio) phthalimide, N-dimethyl-N'-phenol-N '-(fluorodichloromethylthio) sulfamide, 10,10'-
Oxybisphenoxyarsine, 2,2'-methylenebis (4-chlorophenol), 2-methoxycarbonylaminobenzimidazole and the like are blended with the thermoplastic resin to prevent the generation of mold. However, these mildew-proofing agents have a weak mildew-proofing effect alone, and depending on the thermoplastic resin, the processing temperature may be 200 ° C. or higher. There were problems such as evaporation and deterioration of the work environment.

[0003]

The present invention has been made in consideration of such a situation, and has an excellent antifungal effect and does not cause thermal decomposition or evaporation even at a processing temperature of 200 ° C or higher. An object of the present invention is to provide a thermoplastic resin composition containing and a molded article produced from the composition.

[0004]

Means for Solving the Problems The present inventors have found that when a molded product is produced from a resin composition obtained by mixing a thermoplastic resin with various compounds as an antifungal agent, the antifungal agent has heat resistance and evaporation. Of the obtained molded product, it was found that good results were obtained when a specific silicone compound was blended, and further studies were conducted to complete the present invention. .

That is, the present invention is based on the thermoplastic resin 100.
Parts by weight and the following formula I: (In formula, R represents a hydrogen atom or a monovalent hydrocarbon group mutually independently, m is 0-10, n is 1-10, x is 2-.
6, y represents 3 to 10, z represents 0 to 10, and A represents 1
A non-reactive organic polysiloxane-polyoxyalkylene copolymer represented by a divalent hydrocarbon group) 0.1 to 10
The present invention relates to a resin composition for mold resistant and easily washable molded products, which comprises 10 parts by weight.

In the present invention, the thermoplastic resin is, for example, high pressure low density polyethylene, LLDPE, VLDP.
E, HDPE, MDPE, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, acid-modified polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol,
Acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, styrene-butadiene copolymer, methacrylic acid ester copolymer, polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, nitrocellulose,
Ethyl cellulose, butyl cellulose, polyacetal, polyphenylene ether, PPS, POB, PEE
K, polyamideimide, PEG, PPG, chitin / chitosan polymer, alginic acid polymer, fluorine resin, cellulose polymer, protein polymer, polyarylate, polysulfone, PES, PEI, polycaprolactone, thermoplastic elastomer, synthetic rubber, Natural rubber etc. are mentioned.

In the present invention, the non-reactive organic polysiloxane-polyoxyalkylene copolymer is represented by the above formula I. In the above formula I, the groups R and A as monovalent hydrocarbon groups are, for example, alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group,
Octadecyl group, eicosyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), aralkyl group (eg benzyl group, phenylethyl group etc.), tolyl group, xylyl group, cyclohexyl group, halogenated alkyl group (eg trifluoro group) Propyl group, chloropropyl group, etc.) and the like. Examples of the non-reactive organic polysiloxane-polyoxyalkylene copolymer used in the present invention include those represented by the following chemical formula. In the present invention, 0.1 to 10 parts by weight of the non-reactive organic polysiloxane-polyoxyalkylene copolymer is mixed with 100 parts by weight of the thermoplastic resin. When the blending amount of the copolymer is less than 0.1 part by weight, mold resistance is not exhibited,
If it exceeds 10 parts by weight, it will be transferred to the surface of the molded product, and the surface will become sticky and stains will be apt to adhere, which is not desirable.

In addition to the above-mentioned thermoplastic resin and the copolymer represented by the formula I, the resin composition for a mildew-proof and easily washable molded product of the present invention contains, if necessary, an antioxidant and a weather resistance. Property improver, ultraviolet absorber, colorant, pigment, dye, filler, antistatic agent, antifogging agent, crosslinking agent, flame retardant, rust preventive, antibacterial agent, algae preventative, fragrance, plasticizer, processing aid You may mix | blend an agent etc. further.

The resin composition of the present invention is compounded and kneaded with a Banbury mixer, a Henschel mixer, a cokneader, a multi-screw extruder, a ribbon blender, etc., and an extrusion molding machine,
Molded by injection molding machine, compression molding machine, calender molding machine, T die cast molding machine, blow molding machine, rotational molding machine, etc., film, pipe, laminate, rod, plate, tube,
It is a molded product in the shape of a box, container, drum, bottle, or the like.
More specifically, the molded product is a washbasin, a jug, a water supply pipe, a toothbrush, a hairbrush, a comb, a soap dish, a tub, a handle, a handle, a roll, a catheter, a urination bag, an ostomy bag, a blood transfusion bag, a syringe, and a contact. Lens holder, glasses holder, test equipment, food container, food dish, wall material, panel, floor cover, carpet backing, bath mat, telephone handset component, interior material, exterior material, agricultural material, construction material, It means a member for home electric appliances, a member for heavy electric appliances, an automobile article, a wire covering material, a radiator plate for a cooler, a mattress cover, a crib cover, a baby carriage cover, a curtain, a pillow cover, a toy, a keyboard, exercise equipment and the like.

[0010]

EXAMPLES The present invention will now be described in more detail by showing examples of the present invention, but the present invention is not limited to these. Example 1 Linear low density ethylene-hexene-1 copolymer [melt flow rate 2.5 g / 10 min, density 0.920 g / m
l, product name TUF-2060 (manufactured by Nippon Unicar)] 10
The following formula is added to 0 part by weight: 2.5 parts by weight of a polysiloxane-polyoxyalkylene copolymer represented by
The mixture was kneaded at 0 ° C for 10 minutes and pelletized by a granulator. From the pellets, a die slit diameter of 75 mm and a die gap of 1.
5 mm, extrusion temperature 200 ° C., discharge rate 15 kg / hour, frost line 200 mm, expansion amount 2.0, thickness 5
A blown film of 0 μm was obtained. This is 30
Cut into a size of mm × 30 mm, and make a hole with a diameter of 2 mm into 9
A piece was opened and used as a test piece. The test piece was pasted on the agar medium of a Petri dish, and the Bacillus subtilis
ilis) was inoculated and cultured in an incubator set at 28 ° C. for 7 days, but no growth of the bacterium was observed on the test piece.

Example 2 100 parts by weight of polypropylene [melt flow rate 9 g / 10 minutes, density 0.90 g / ml, trade name F209B (manufactured by Tonen Polypro)] were added with the following formula: 0.5 parts by weight of a polysiloxane-polyoxyalkylene copolymer represented by
The mixture was kneaded at 0 ° C for 10 minutes and pelletized by a granulator. Using an air-cooled inflation film molding device from these pellets, an inflation film having a diameter of a die slit of 100 mm, a die gap of 1.2 mm, an extrusion temperature of 220 ° C., a discharge rate of 12 kg / hour, a frost line of 150 mm, and an expansion rate of 1.7 and a thickness of 30 μm are blown. I got a film. This was cut into a size of 30 mm × 30 mm, and 9 holes having a diameter of 2 mm were opened to obtain a test piece. Paste this test piece on the agar medium of a Petri dish, and put it on Aspergillus terreus (Asp
ergillus terreus) was inoculated and cultured in an incubator set at 28 ° C. for 7 days, but the growth of the bacterium was not observed on the test piece.

Example 3 100 parts by weight of nylon 66 [trade name LEONA1300S (made by Asahi Kasei)] has the following formula: 0.2 parts by weight of a polysiloxane-polyoxyalkylene copolymer represented by the above formula was blended, kneaded by an extruder at 260 ° C., and pelletized by a granulator. A plate having a thickness of 0.5 mm was prepared from the pellets by an injection molding machine at 280 ° C., the plate was cut into a size of 30 mm × 30 mm, and 9 holes having a diameter of 2 mm were punched to obtain test pieces. This test piece was pasted on an agar medium of a Petri dish, inoculated with Penicillium citrinum strain, and cultured for 7 days in an incubator set at 28 ° C. I was not able to admit.

Comparative Example 1 N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) sulfide was used as a fungicide in place of the polysiloxane-polyoxyalkylene copolymer used in Example 3. When the same experiment as in Example 3 was performed, the test piece was covered with the fungal layer after 7 days of culture. This is because the antifungal agent used was thermally decomposed at a high temperature of 280 ° C. and the antifungal effect was lost.

Easy washability test A line was drawn on the test piece obtained in Example 1 with an oil-based black pen, and 2
After leaving it at room temperature for 4 hours, it was wiped off with a wet cloth and the condition of the coating film was observed, but no stain remained.
A similar test was conducted on the test pieces obtained in Examples 2 and 3, but no stain remained on them. For comparison, when the above test was conducted using a test piece produced without blending the polysiloxane-polyoxyalkylene copolymer, a considerable amount of stain remained.

Example 4 High-pressure low-density polyethylene [melt index 1.3
g / 10 minutes, density 0.920 g / ml, trade name DND-
2450 (manufactured by Nihon Unicar)] 2.8 parts by weight of the polysiloxane-polyoxyalkylene copolymer represented by the above formula was blended, kneaded at 150 ° C. with a Banbury mixer, and pelletized with a granulator. The pellets were injection molded at 170 ° C by an injection molding machine,
A cutting board of cm × 20 cm × 2 cm was prepared. This one
It was used for a year, but no mold was found.

Comparative Example 2 The same experiment as in Example 4 was carried out except that the polysiloxane-polyoxyalkylene copolymer used in Example 4 was not used. After 3 months, the mold on the cutting edge of the cutting board had mold. Occurred and became black.

[0017]

The resin composition of the present invention comprises a thermoplastic resin and a specific polysiloxane-polyoxyalkylene copolymer as a mildew-proofing agent, which is nontoxic to the human body and is molded at high temperature. Even if the antifungal agent is not thermally decomposed or evaporated, the antifungal effect is not lost and the working environment is not deteriorated. Therefore, the resin composition of the present invention is particularly useful as a material for foods and medical moldings. Further, the molded product of the present invention can be easily washed off even if ink or other stains are attached, the aesthetic appearance of the molded product is maintained, and the molded product can be used for a long time.

Claims (2)

[Claims] 1. 100 parts by weight of a thermoplastic resin and the following formula I: (In formula, R represents a hydrogen atom or a monovalent hydrocarbon group mutually independently, m is 0-10, n is 1-10, x is 2-.
6, y represents 3 to 10, z represents 0 to 10, and A represents 1
A non-reactive organic polysiloxane-polyoxyalkylene copolymer represented by a divalent hydrocarbon group) 0.1 to 10
A resin composition for moldable and easily washable molded products, which comprises 10 parts by weight. 2. A mold-proof and easily washable molded product produced from the resin composition according to claim 1.