JP2865742B2 - Anti-mite thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] <Industrial application field> The present invention effectively exhibits anti-mite properties, specifically, repellent mite properties, and is excellent in hue, weather resistance, and heat aging resistance. And a highly safe thermoplastic resin composition.

<Prior art> Conventionally, thermoplastic resins have been used widely and widely by utilizing their excellent properties because of their excellent mechanical properties and excellent moldability. So it is a material that we must live in.

Specifically, these thermoplastic resins are formed into clothing and housing articles, for example, tatami mats, jutans, carpets, blankets, and the like, and are indispensable for living a comfortable modern life.

However, in recent years, homes have been equipped with air-conditioning and heating systems, and while creating comfortable living spaces, mites have also been created in a state where they can easily propagate. Therefore, the occurrence of ticks becomes a problem even in the winter season, and various measures against ticks are being implemented.

However, such ticks can cause the entire house to be unsanitary, because it can grow and live on various floors such as houses and hospitals, especially on tatami mats, jutans, carpets, clothing, blankets, etc. It is hated as one of the causes of Zensoku.

Therefore, creating a tick-free residential environment is extremely important for sanitation in our lives.

Conventionally, as acaricides used for exterminating mites, drugs using compounds such as pyrethroids, organophosphates, carbamates, and the like are known, and these drugs are sprayed by a method such as spraying and used. doing. However, these drugs were toxic and had safety problems, and their effects were temporary.

JP-A-61-87603 proposes a mite control material in which benzyl salicylate or phenethyl benzoate is contained in polypropylene or an acrylic resin to form a carpet pile or a primary base cloth.

<Problems to be Solved by the Invention> However, the proposal using polypropylene or an acrylic resin containing only benzyl salicylate or phenethyl benzoate has an effect of miticide properties, and the repellent mite property is not clear. Neither is it an effective method for repelling mites.

[Summary of the Invention]

<Summary> As a result of intensive studies in view of the above problems, the present inventors have found that a composition in which a specific compound and a specific light stabilizer are combined into a specific amount of a thermoplastic resin has remarkable weather resistance. The present invention was found to have improved hue, good hue and heat aging resistance, and was found to be able to exhibit repellent mites.

That is, the anti-mite thermoplastic resin composition according to the present invention comprises 100 parts by weight of a thermoplastic resin, 0.1 to 10 parts by weight of pt-butylphenyl salicylate and / or p-octylphenyl salicylate, and a hindered amine having a molecular weight of 500 or more. It is characterized by comprising 0.001 to 1 part by weight of a light stabilizer.

<Effect> The anti-mite thermoplastic resin composition of the present invention has a low danger by retaining a specific compound and a specific light stabilizer, and can maintain repellent mite properties for a long time. Since it is excellent in weather resistance, hue, and heat aging resistance, it can be used for various housing articles and the like to provide a healthy and comfortable life without mites.

[Specific description of the invention]

[I] Anti-mite thermoplastic resin composition (1) Constituents (a) Thermoplastic resin As the thermoplastic resin used in the anti-mite thermoplastic resin composition of the present invention, polyethylene, polypropylene, poly-4- Methylpentene-1, polybutene-
Polyolefin resins such as 1, polystyrene, acrylonitrile / styrene (AS) resin; acrylonitrile /
Butadiene styrene (ABS) resin, polyphenylene ether (PPE) resin, polyacrylonitrile, fluororesin, polymethacrylstyrene, methacrylic resin, polyamide resin, polyethylene terephthalate, polybutylene terephthalate, polycarbonate resin, polyvinyl alcohol, polyacetal, hydroxybenzoic acid polyester And the like.

Preferred among these thermoplastic resins are polyolefin resins, specifically, low-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene,
Medium density polyethylene, high density polyethylene, propylene homopolymer, propylene / ethylene random and block copolymer, propylene / ethylene-1-butene copolymer, propylene-1-butene copolymer, poly-4-methylpentene- And most preferably propylene homopolymer, propylene / ethylene random and block copolymers. The melt flow rate (MFR) of these resins (JIS K7210, 230 ° C., 2.16 kg) is preferably from 0.1 to 100 g / 10 minutes, and particularly preferably from 0.5 to 80 g / 10 minutes because of good moldability.

(B) Compound In the anti-mite thermoplastic resin composition of the present invention, p
It is important to incorporate -t-butylphenyl salicylate and / or p-octylphenyl salicylate.

The addition amount of such a compound is the same as that of the thermoplastic resin 100.
0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, most preferably 0.3 to 3 parts by weight with respect to parts by weight. If it is less than the above range, the anti-mite property and weather resistance are insufficient, and if it exceeds the above range, not only is it uneconomical, but also it causes problems such as bleeding, which is not preferable.

(C) Hindered amine light stabilizer In the anti-mite thermoplastic resin composition of the present invention, it is important to incorporate a hindered amine light stabilizer having a molecular weight of 500 or more, preferably 700 or more.

Specific examples include the following hindered amine-based light stabilizers, but are not limited thereto.

(1) Polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine (2) Poly [[6- (1,1,3 , 3-tetramethylbutyl)
Imino-1,3,5-triazine-2,4-diyl] [(2,2,6,
6-tetramethyl-4-piperidyl) imino] hexamethylene [[2,2,6,6-tetramethyl-4-piperidyl)
Imino]] (3) Bis (1,2,2,6,6) of 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid
-Pentamethyl-4-piperidyl) ester (4) tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate (5) bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate (6) Polycondensation of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 1,2-dibromoethane (7) Poly [2-N, N'-bis (2,2,6,6-teramethyl-
4-piperidyl) hexamethylenediamine-4- (N-
Morpholino) simtriazine] (8) 1,1 ′-(1,2-ethanediyl) -bis (3,3,5,5
-Tetramethylpiperazinone) (9) Tris (2,2,6,6-tetramethyl-4-piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate (10) Tris (1,2 , 2,6,6-pentanemethyl-4-piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate.

The most suitable compounds among these are (1),
(2), (4) and (7).

The compounding amount of the hindered amine light stabilizer of the component (C) is 0.001 to 1 part by weight, preferably 0.02 to 0.5 part by weight, per 100 parts by weight of the thermoplastic resin.

When the amount of the component (C) is less than the above range, the heat aging resistance and hue of the present resin composition are not sufficient. When the amount exceeds the above range, not only is uneconomical problem but also discoloration problem and bleed problem are caused. It is not preferable because it occurs.

If the molecular weight is less than 500, the effect of the present invention cannot be exhibited due to a change in surface characteristics due to the bleed, in addition to the problem of the bleed itself.

(D) Other compounding components In addition to these components, other additional components can be compounded in the anti-mite thermoplastic resin composition of the present invention within a range that does not significantly impair the effects of the present invention. For example, phenol-based, phosphorus-based, sulfur-based antioxidants, organic or inorganic nucleating agents, ultraviolet absorbers, nickel- or benzoate-based light stabilizers, amide-based or silicone oil-based lubricants Glycerin, fatty acid ester type, amine type, amide type, etc. antistatic agent, molecular weight regulator such as peroxide, foaming agent, organic or inorganic pigment, dispersant, metal salt type neutralizing agent, antacid Agents, fluorescent brighteners, inorganic or organic antibacterial agents and fungicides, organic or inorganic fillers, adsorbents, flame retardants and the like. It is particularly preferable to use an antistatic agent in combination among these additives from the viewpoint of improving the hue.

In addition, a combination of an acaricide and an anti-mite agent is also possible, and a synergistic effect can be expected.

(2) Production of composition The anti-mite resin composition of the present invention can be produced by blending the above-mentioned components by a usual method.

Specifically, each of the above components and other components are added to the powder of the thermoplastic resin and, if necessary, mixed with a Henschel mixer or the like, and then extruded by melt-kneading with an extruder or the like, An anti-mite thermoplastic resin composition in the form of pellets.

(3) Forming process Thereafter, the pellets are processed into a target container or fiber by a molding machine such as injection molding, compression molding, sheet, yarn molding, film molding, blow molding, vacuum molding, spinning, and nonwoven fabric molding. In general, a method may be used in which a masterbatch in which the above-mentioned components are blended at a high concentration is prepared, and the masterbatch is diluted at the time of molding to make the concentration range of the anti-mite composition of the present invention.

(4) Molded product Examples of molded products obtained by the molding method include vacuum cleaner parts, air conditioner / cooler parts, cars,
Molded articles for vehicles such as trains, storage boxes for containers, clothing, etc., underlays in closets, carpets, sofas, bedding,
Tatami, filter nets, food storage, tableware storage, closets, clothing, agricultural equipment parts and the like can be mentioned. In particular, it is preferable to form a molded article in a house or a vehicle.

Particularly preferred molded articles include injection molded articles for storage and the like, yarn molded articles for sheets and carpet base fabrics, and spun and nonwoven molded articles such as carpets. Most preferred are injection molded articles.

〔Example〕

Examples 1 to 5 and Comparative Examples 1 to 4 MFR = 9 g / 10 minutes, 100 parts by weight of a propylene / ethylene block copolymer having an ethylene content of 5% by weight were mixed with the following compound, and stirred with a Henschel mixer. The mixture was kneaded with an extruder (set at 230 ° C.) to form pellets.

Next, the pellets were applied to an injection molding machine (set at 240 ° C.) to produce test pieces of 120 mm × 90 mm × 2 mmt. And the following evaluation was performed using this test piece.

 Table 1 shows the results.

<Weather resistance> The injection test piece was subjected to a xenon type weather tester (black panel temperature: 63 ° C., rainfall: 12 minutes / 6 minutes cycle), and the crack generation time was determined with a 60 × microscope.

<Hue> The sample placed on the tester was taken out for 48 hours and 100 hours, and the change in hue was visually observed.

 The visual criteria are shown below.

ほ と ん ど Almost unchanged ○ Can be used slightly changed but usable △ Discolored × Discolored considerably <Heat aging resistance> The injection test piece was placed in a gear oven set at 120 ° C., and the time until embrittlement was measured.

<Anti-mite test> (Specimen) A 2 mmt injection piece measuring 9 cm x 12 cm was used.

(Used mites) Dermatophagoides farinae (Experimental method) At the bottom of a polybat, 11 cm high, 40 cm wide and 30 cm long, 150 g of powdered feed (mice, for latch rearing, CE-2, manufactured by Nippon Clea Co., Ltd.) can be made on the bottom of a polybat. The sample was spread evenly, and samples cut into a size of 9 cm × 12 cm were placed on the left and right one by one. One of the left and right samples was an insect repellent sample and the other was a control sample.

A sample containing 2.5 g of powdered mite-free powder (water content: 15%) was placed in a container having a height of 1.4 cm and a diameter of 2.8 cm in the center of the specimen, and one day later, the specimen was crawled into the food. The number of mites was counted by the saline floating method. In the saline floating method, after thoroughly mixing the feed for mites crawling, take out 0.5 g of it, place it in a Wildman flask, suspend the mites using 20% saline, and suction the water in the upper layer. It was transferred onto a filter paper equipped with a device, filtered, and the filter paper was stained with a 0.1% aqueous methylene blue solution. As a result of this operation, only the filter paper is dyed blue, and the mites are not dyed but appear yellowish white,
The total number was counted under a stereomicroscope.

The repellent effect (%) was calculated from the number of mites observed in the insect repellent sample and the control sample in the same polybat using the following formula.

(Experimental Results) The test was performed at a room temperature of 25 ° C. ± 2 ° C. and a related temperature of 70 to 80%.

Table 1 shows the results of observing the repellent effect of each sample on Dermatophagoides farinae. Each is the average of the results of three repeated experiments.

 Here, the repelling effect was based on the following criteria.

◎:> 60% ○: 60 to 40% △: 40> to 20% ×: <20% <Compound name> (repellent mite compound) (A): Phenyl salicylate (B): pt-butylphenyl salicylate (C): p-octylphenyl salicylate (hindered amine light stabilizer) (1) Weight of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine Condensate, molecular weight: 3000 or more (2) Poly [[6- (1,1,3,3-tetramethylbutyl)
Imino-1,3,5-triazine-2,4-diyl] [(2,2,6,
6-tetramethyl-4-piperidyl) imino] hexamethylene [2,2,6,6-tetramethyl-4-piperidyl) imino]], molecular weight: 2500 or more (3) tetrakis (2,2,6,6- Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, molecular weight: 790 (4) Poly [2-N, N'-bis (2,2,6,6-tetramethyl-4-) Piperidyl) hexamethylenediamine-4- (N
-Morpholino) simtriazine], molecular weight: 1500 or more (5) LS770: 2,2,6,6-tetramethylpiperidyl sebacate, molecular weight = 480.7 (other additives) M329: tris (mixed, mono and dinonyl) Phenyl) phosphite IR1010: tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane CAST: calcium stearate TS5: glycerin monostearate

Continuation of the front page (56) References JP-A-61-87603 (JP, A) JP-A-62-33106 (JP, A) JP-A-64-19004 (JP, A) JP-A-63-22845 (JP) JP-A-63-175072 (JP, A) JP-A-64-24733 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A01N 37/10 CA (STN) REGISTRY (STN) WPI (DIALOG)

Claims (1)

(57) [Claims] (1) 100 parts by weight of a thermoplastic resin, 0.1 to 10 parts by weight of pt-butylphenyl salicylate and / or p-octylphenyl salicylate, and 0.001 to 1 part by weight of a hindered amine light stabilizer having a molecular weight of 500 or more. An anti-mite thermoplastic resin composition, comprising: