JPH03153601A - Miteproof thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition good in hue, weatherability and heat deterioration resistance, high in safety, effective when processed and formed into clothes, etc., by incorporating a thermoplastic resin with, as active ingredients, a specific compound and hindered amine-based light stabilizer at each specified proportion. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100 pts.wt. of a thermoplastic resin with (B) 0.1-10 pts.wt. of a compound of the formula (n R<1> are same or different groups selected from hydroxyl group and 1-9C hydrocarbon groups; R<2> is H or 1-30C hydrocarbon group; where the hydrocarbon groups for both R<1> and R<2> may contain hetero atoms; X is H or hydroxyl group; n is 0-4) (pref. p-t-butylphenylsalicylate or p-t- octylphenylsalicylate) and (C) 0.001-1 pt.wt. of a hindered amine-based light stabilizer >=500 in molecular weight, e.g. a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine.

Description

[Detailed description of the invention] [Background of the invention] The present invention relates to a highly safe thermoplastic resin composition.

<Conventional technology> Thermoplastic resins have traditionally had excellent mechanical properties and excellent moldability, so they have come to be widely used by taking advantage of each of their excellent properties, and are now widely used. It has become an indispensable material in our daily lives.

Specifically, these thermoplastic resins are used in clothing, household goods,
For example, it is molded into tatami mats, carpets, blankets, etc., and has become an essential part of living a comfortable modern life.

However, in recent years, homes have been equipped with air conditioning and heating systems, which have created comfortable living spaces, but have also created conditions that make it easier for dust mites to breed.

Therefore, the occurrence of mites becomes a problem even in winter, and various measures against mites are being implemented.

However, these mites live and grow in various places such as floors of houses and hospitals, especially tatami mats, carpets, car vents, clothes, blankets, etc., making the whole house unsanitary and causing harm to children. It is hated as one of the causes of Zensoku.

Therefore, creating a housing environment free of ticks is extremely important for hygiene in our lives.

Traditionally, acaricides used to exterminate ticks include chemicals using compounds such as pyrethroids, axes, and carbamates, and these chemicals are applied by spraying or other methods. , are using. However, these drugs were highly toxic and had safety problems, and their effects were only temporary.

Japanese Unexamined Patent Publication No. 61-87603 proposes a mite control material in which benzyl salicylate or phenethyl benzoate is impregnated with polypropylene or acrylic resin and molded into carpet pile or primary base fabric.

<Problems to be Solved by the Invention> However, the proposed product using polypropylene or acrylic resin containing only benzyl salicylate or phenethyl benzoate has a miticide effect, and its mite repellency is not certain. Furthermore, it cannot be said to be an effective method for repelling mites.

[Invention! Essential]

Summary> As a result of intensive research in view of the above problems, the present inventor has discovered that
A composition in which a specific compound and a specific light stabilizer are combined and blended into a specific amount of thermoplastic resin has significantly improved weather resistance, good hue and heat aging resistance, and has good mite repellency. The present invention was completed based on the knowledge that this can be achieved.

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 a compound represented by the following formula (1), and a hindered amine photostable resin having a molecular weight of 500 or more. It is characterized by comprising 0.001 to 1 part by weight of the agent.

(R1 in the formula is a single or different group selected from a hydroxyl group and a hydrocarbon group having 1 to 9 carbon atoms, and R2 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ,
The hydrocarbon groups of R1 and R2 may contain heteroatoms. X is hydrogen or a hydroxyl group. n represents an integer from 0 to 4. ) Effect> By incorporating a specific compound and a specific light stabilizer, the anti-mite thermoplastic resin composition of the present invention is less dangerous and can maintain mite-repelling properties for a long time, Furthermore, since it has excellent weather resistance, color [1l111111] heat aging resistance, it can be molded and used in various household goods, etc., so that it can lead to a healthy and comfortable life without the occurrence of dust mites.

[Detailed description of the invention]

(1) Anti-mite thermoplastic resin composition (1) Component (a) Thermoplastic resin The thermoplastic resin used in the anti-mite thermoplastic resin composition of the present invention includes polyethylene, polypropylene, poly-4- Methylpentene-1, polybutene-1,
Polyolefin resins such as polystyrene, acrylonitrile styrene (AS) resin; acrylonitrile butadiene styrene (ABS) resin, polyphenylene ether (PPO) 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,
These include propylene-1-butene copolymer, poly-4-methylpentene-1, etc., and most preferably propylene homopolymer, propylene-e-ethylene random and block copolymer. The melt flow rate (M
FR) (JIS K7210.230℃, 2.16k
g) is 0. 1-100. /10 minutes is preferable,
Particularly, 0.5 to 80 g/10 minutes is preferable because moldability is good.

(b) Compound In the anti-mite thermoplastic resin composition of the present invention, it is important to blend the compound of the following formula [1].

(R1 in the formula is a single or different group selected from a hydroxyl group and a hydrocarbon group having 1 to 9 carbon atoms, and R2 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ,
The hydrocarbon groups R and R2 may contain heteroatoms. X is hydrogen or a hydroxyl group. n represents an integer from 0 to 4. ) Specific examples of the above compounds include methyl benzoate, ethyl benzoate, phenyl benzoate, benzyl benzoate, phenethyl benzoate, salicylic acid, methyl salicylate, ethyl salicylate, phenyl salicylate,
Examples include benzyl salicylate, pt-butylphenisalicylate, p-octylphenyl salicylate, and the like. Preferred compounds among these are salicylic acid ester compounds, and more preferred are p-
These are t-butylphenyl salicylate and pt-octylphenyl salicylate.

The amount of such a compound added is 100% of the thermoplastic resin.
0.1 to 10 parts by weight, preferably 0.2 parts by weight
-5 parts by weight, most preferably 0.3-3 parts by weight. If it is less than the above range, the anti-mite properties and weather resistance will be insufficient.
Exceeding the above range is not only uneconomical but also causes problems such as bleeding, which is undesirable.

(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.

Specifically, the hindered amine light stabilizers shown below can be mentioned, but are not limited thereto.

(1) Polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-titramethylpiveridine (2) Poly[[6-(1,1 ,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diylco[(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[[2,2 ,6,6-tetramethyl-4-piperidyl)imino]] (3) Bis(1,2
,2,6,6-bentamethyl-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) N,N'-bis(2,2,6,6-tetramethyl 4-piperidyl)hexamethylenediamine and 1,2-
Polycondensate with dibromoethane (7) Poly [2-N, N
'-bis(2,2,6゜6-tetramethyl-4-piperidyl)hexamethylenediamine-4-(N-morpholino)simtriazineco(8)1.1'-(1,2-ethanediyl)bis (
3,3,5,5-tetramethylpiperazinone) (9) Tris(2,2,6,6-tetramethyl-4-peviridyl)-dodecyl-1,2,3,4-butanetetracarboxylate ( 10) Tris(1,2,2,6,6-peranemethyl-
Examples include 4-piperidyl)-dodecyl-1,2°3,4-butanetetracarboxylate.

The most suitable compound among these is (1) above.

These are the compounds (2), (4), and (7).

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

If the blending amount of component (C) is less than the above range, the heat aging resistance and color tit of the resin composition will not be sufficient, and if it exceeds the above range, it will not only be uneconomical but also cause discoloration and bleeding problems. This is not desirable.

Moreover, if the molecular weight is less than 500, not only the problem of bleeding itself but also the change in surface characteristics due to bleeding makes it impossible to exhibit the effects of the present invention.

(d) Other ingredients In addition to these ingredients, other additional ingredients may be added to the anti-mite thermoplastic resin composition of the present invention within a range that does not significantly impair the effects of the invention. For example, phenol-based, phosphorus-based, sulfur-based antioxidants, organic or inorganic nucleating agents, ultraviolet absorbers, nickel-based or benzoate-based light stabilizers, amide-based or silicone oil-based lubricants, etc. , antistatic agents such as fatty acid esters of glycerin, amines, and amide types, molecules such as peroxides, etc.
fi adjuster, foaming agent, organic or inorganic pigment, dispersant, metal salt neutralizing agent, antacid, fluorescent brightener, inorganic or existing antibacterial/fungal agent, organic or Examples include inorganic fillers, adsorbents, and flame retardants. Among these compounding agents, it is particularly preferable to use an antistatic agent in combination in order to improve the hue.

It is also possible to use acaricides and anti-mite agents in combination, and a synergistic effect can be expected.

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

Specifically, each of the above components and other components as necessary are added to a thermoplastic resin powder, mixed with stirring using a Henschel type mixer, etc., and then melted and kneaded using an extruder or the like and extruded. A pellet-shaped anti-mite thermoplastic resin composition is prepared.

(3) Molding process After that, this pellet is injection molded, compression molded, sheeted,
Generally, it is processed into desired containers, fibers, etc. using forming machines such as yarn forming, film forming, blow molding, vacuum forming, spinning, and nonwoven fabric forming. Alternatively, a masterbatch may be prepared and diluted during molding to achieve a concentration range of the anti-mite composition of the present invention.

(4) Molded products Examples of molded products obtained by the above molding method include:
Vacuum cleaner parts, air conditioner/cooler parts, molded parts for vehicles such as cars and trains, containers, storage boxes for clothing, underlays for closets, carpets, sofas, tatami mats, filter nets, food storage Examples include warehouses, tableware storage, cupboards, clothing, agricultural equipment parts, etc. In particular, it is suitable to use as a molded product for use inside a house or a vehicle.

Particularly preferred molded products include injection molded products for storage, sheets, yarn molded products for carpet base fabrics, and spun and nonwoven fabric molded products for carpets. Most preferred are injection molded articles.

[Experiment example]

Examples 1 to 5 and Comparative Examples 1 to 5 The following compounds were blended into 100 parts by weight of propylene/ethylene block copolymer with an ethylene content of 5% by weight in MFR-9 for 10 minutes, and the mixture was stirred with a Henschel mixer. After that, the mixture was kneaded in a 30mriφ extruder (set at 230°C) to form pellets.

Next, this pellet was placed in an injection molding machine (set at 240°C) to produce a test piece measuring 120III 11 x 90 x 2 mm. The following evaluations were performed using this sample.

The results are shown in Table 1.

Weather Resistance> The injection test piece was subjected to a xenon type weather tester (black panel temperature 63°C, rain 12 minutes/6 minutes cycle), and the crack generation time was determined using a 60x microscope.

Hue> The samples applied to the tester were taken out after 48 hours and 100 hours, and changes in hue were visually observed.

The visual criteria are shown below.

◎ Almost no change 0 Slight discoloration but usable Δ Discoloration × Considerable discoloration and 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> (sample) A 2 mm thick injection sheet measuring 9 cm x 12 (to) was used.

(Mites used) Dermatophagoides nigricans (Experimental method) Powdered feed (for mouse, latch rearing,
CE-2 (manufactured by Nippon Flare Co., Ltd.) 150sr was spread as uniformly as possible, and a specimen cut to the size of 9c+nX12 countries was placed on top of this, one on each side.

One of the left and right specimens was an insect control specimen, and the other was a control specimen.

On this specimen, a container with a height of 1.4 marks and a diameter of 2.8 marks in the center contains powdered feed (moisture 15%) containing no mites.2.
After 1 hour, the number of mites that had entered the feed was counted using the saline flotation method. In the saline suspension method, after stirring the tick crawler feed well, take out 0.5 g of it, put it in a Wildman flask, and add 20%
The mites are suspended in saline solution, the upper layer of water is transferred onto a filter paper equipped with a suction device, filtered, and the filter paper is reduced to 0.1%.
It was stained with a methylene blue aqueous solution. With this operation,
Only the filter paper was stained blue, and the mites were not stained and appeared yellowish and white, so the total number of mites was counted under a stereomicroscope.

The repellent effect is calculated by calculating the repellency rate (
%) was calculated.

(Experimental Results) The test was conducted at a room temperature of 25° C.±2° C., within a relative temperature range of 70 to 80%.

Table 1 shows the results of observing the repellent effect of each specimen on the mites. All results are the average of the results of three repeated experiments.

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

◎: 〉60% O: 60-40% Δ: 40〉-20% Salicylate (C)
: p-Octylphenyl salicylate (D): Benzyl salicylate (hinidadamine light stabilizer) (1) Dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-titramethylbisuccinate Polycondensate with veridine, 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]], molecule i:
2500 or more (3) Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1. 2. 3.4-
Butane tetracarboxylate, molecule ffinia 90 (
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-titramethylpiveridyl sebacate, molecule m-480,7 (other additives) M329 Nidris (mixed, mono and dinonylphenyl) phosphite IRIOIO: Tetrakis [methylene-3-(3',
5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane CAST Calcium nistearate TS5: Glyceryl monostearate

Claims (1)

[Scope of Claims] From 100 parts by weight of a thermoplastic resin, 0.1 to 10 parts by weight of a compound represented by the following formula [I], 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. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (R^1 in the formula is a single or different group selected from a hydroxyl group and a hydrocarbon group having 1 to 9 carbon atoms, and R^2 is hydrogen It is an atom or a hydrocarbon group having 1 to 30 carbon atoms.However, the hydrocarbon group of R^1 and R^2 may contain a heteroatom.X is hydrogen or a hydroxyl group.n is 0
Represents an integer from ~4. )