JPH0721092B2 - Polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyolefin resin composition having excellent insect repellent properties.

[Conventional technology]

Polyolefin resins are widely used in miscellaneous goods containers, packaging containers, and industrial parts because of their excellent mechanical properties, chemical properties, and hygiene.

In particular, it is suitable for mass production because it can be easily molded, and since it is possible to easily process a material that is difficult to form or has a difficult shape with conventional materials, its application is further expanded.

Therefore, the application of these polyolefin resins to kitchen appliances, such as housing materials for household appliances, other containers, sinks and their outer and inner surface materials, or floor materials, wall materials, ceiling materials, etc. is also remarkable. Is increasing.

Similarly, it is also actively used for clothes storage cases and chests. For example, these must always be hygienic for kitchen utensils, and the pests must be protected from the pests of clothes in case of clothes.

Pesticides and catching devices are used for these purposes.

[Problems to be Solved by the Invention] However, these are harmful to the human body, the odor is transferred to foods and clothes, the appearance is unpleasant, and the duration of the effect is short. It was troublesome to replace it frequently.

For this reason, if there is a material that is odorless, safe for the human body, and effective against insects, it is expected to have great utility value without the above problems.

[Means and Actions for Solving Problems]

The inventors of the present invention have completed the present invention by finding that it is sufficient to use an organic compound having a specific insect repellent property, for the purpose of imparting an excellent insect repellent effect to the above-mentioned hygienic and odorless polyolefin resin. I have arrived.

That is, the present invention relates to the general formula (I) based on 100 parts by weight of the polyolefin resin. (In the formula, X represents an oxygen atom or —CH ₂ —, Y represents a hydrogen atom or a fluorine atom.) A polyolefin resin composition comprising 0.0001 to 10 parts by weight of an organic compound represented by the formula: The polyolefin resin composition according to the present invention has excellent insect repellent properties that repel and kill harmful insects.

The polyolefin resin used in the present invention includes high density polyethylene, low density polyethylene, medium density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, polybutene-1, poly-4-methylpentene-1 and the like. These may be used alone or in combination. It may also contain other resins.

The insect-repellent organic compound used in the present invention is represented by the general formula (I), and these compounds are disclosed in JP-A-58-32840.
No. 58-118533, 58-201737, it is easily manufactured.

The addition amount of these is 0.0001 to 10 parts by weight, preferably 0.00
It is 1 to 2 parts by weight. Addition of less than 0.0001 parts by weight has almost no effect on imparting the insect-repellent property of the polyolefin resin, and
Even if added in excess of 10 parts by weight, the effect is not significantly increased and the cost becomes economically high.

The resin composition of the present invention may optionally contain other additives such as neutralizing agents such as calcium stearate, magnesium hydroxide and aluminum hydroxide, and 2,6-di-t-butyl-4.
-Methylphenol, n-octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, pentaerythyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tetrakis (2,4-di-t-) Butylphenyl) 4,
4'-biphenylene diphosphonate, tris (2,4-di-
Antioxidants such as t-butylphenyl) phosphite, dilauryl thiobipropionate, distearyl thiodipropionate, 2- (3-t-butyl-5-methyl-2)
-Hydroxyphenyl) -5-chlorobenzotriazole, bis (2,2,6,6-tetramethyl-4-piperidyl)
UV absorbers such as sebacate, glycerin monostearate, stearyl alcohol, antistatic agents such as bis- (2-hydroxytaloamine), pt-butyl benzoic acid aluminum salt, dibenzylidene sorbitol, 1,3
Crystal nucleating agent such as -2,4-di (ethylbenzylidene) sorbitol, pigment, dispersant such as zinc stearate, peroxide, talc, calcium carbonate, barium sulfate, glass fiber, mica, inorganic such as calcium silicate A filler or the like can be added within a range not impairing the insect repellent effect.

The resin composition of the present invention is a polyolefin resin, an organic compound represented by the general formula (I), and if necessary, other additives are mixed and uniformly dispersed by a Henschel mixer, another blender, etc., and melted by an extruder. It can be obtained by pelletizing.

The polyolefin resin composition of the present invention is excellent in hygiene and odorlessness, and has an excellent insect repellent effect, which is injection molded or blow molded, sheet molded, vacuum molded,
Widely effective for food storage, tableware storage, various cabinets, clothes storage boxes, wardrobes for costumes, flowerpots, wall materials, flooring materials, ceiling materials, and other applications by molding using various molding methods such as compression molding. It can be used for. That is, the container, device, and the like using the polyolefin resin of the present invention have the effect of repelling harmful insects and not attracting them, and killing harmful insects even if they become dusty, and this effect lasts for a long time.

〔Example〕

 Hereinafter, the details of the present invention will be described with reference to examples.

Examples 1 to 3 Polypropylene [Mitsui Noblene JHH (trademark; manufactured by Mitsui Toatsu Chemicals, Inc.)] powder 100 parts by weight, 2,6-di-t-butyl-p-cresol 0.05 part by weight, pentaerythyl-
Tetrakis [3-3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, calcium stearate 0.1 part by weight, glycerin monostearate
0.2 parts by weight, bis- (2-hydroxytaloamine) 0.1
3-phenoxybenzyl 2- (4-ethoxyphenyl) -2-methylpropyl ether to 0.1 part by weight of stearyl alcohol and 0.1 (example 1), 0.5 (example 2) and 1.0 (example 3), respectively. Part and add it in a Henschel mixer and use an ordinary extruder to extrude about 220
A 160 mm × 160 mm × 2 mm flat plate was molded from the pelletized product at ℃ using an injection molding machine at an injection molding temperature of about 220 ℃.

The insect repellent effect of the obtained flat plate was evaluated.

Insect repellent effect is 90mmφ × 90 on the polypropylene plate
A 10 mm cockroach male was placed in a petri dish over a mm petri dish and the number of lateral worms was examined at each elapsed time.

The results are shown in Table-1.

Examples 4 to 6 In Examples 1 to 3, 3-phenoxybenzyl 2-
3-phenoxy-4-fluorobenzyl 2-instead of (4-ethoxyphenyl) -2-methylpropyl ether
(4-Ethoxyphenyl) -2-methylpropyl ether was molded in the same manner as in Examples 1 to 3 except that 0.1 (Example 4), 0.5 (Example 5), and 1.0 (Example 6) parts by weight, respectively, were used. To obtain a flat plate. The same evaluation was performed below.

The results are shown in Table-1.

Examples 7-9 In Examples 1-3, 3-phenoxybenzyl 2-
Instead of (4-ethoxyphenyl) -2-methylpropyl ether, 1- (3-phenoxyphenyl) -4-
(4-ethoxyphenyl) -4-methylpentane respectively
0.1 (Example 7), 0.5 (Example 8), 1.0 (Example 9)
A flat plate was obtained by molding in the same manner as in Examples 1 to 3 except that the parts by weight were used. The same evaluation was performed below.

The results are shown in Table-1.

Examples 10 to 12 In Examples 1 to 3, 3-phenoxybenzyl 2-
Instead of (4-ethoxyphenyl) -2-methylpropyl ether, 1- (3-phenoxy-4-fluorophenyl) -4- (4-ethoxyphenyl) -4-methylpentane was added to 0.1 (Example 10), respectively. , 0.5 (Example 11), 1.0
(Example 12) A flat plate was obtained by molding in the same manner as in Examples 1 to 3 except that parts by weight were used.

The same evaluation was performed below.

The results are shown in Table-1.

Comparative Example 1 In Example 1, 3-phenoxybenzyl 2- (4-
A slab was obtained by performing the same molding except that ethoxyphenyl) -2-methylpropyl ether was not added.

The same evaluation was performed below.

The results are shown in Table-1.

Comparative Example 2 In Example 3, 3-phenoxybenzyl 2- (4-
Ethoxyphenyl) -2-methylpropyl ether 2,
A flat plate was obtained by replacing the 4,4'-trichloro-2'-hydroxyphenyl ether with the same molding.

Hereinafter, the same evaluation was performed.

The results are shown in Table-1.

Comparative Example 3 In Example 3, 3-phenoxybenzyl 2- (4-
(Ethoxyphenyl) -2-methylpropyl ether was replaced with (2-isopropyl-4-methylpyridyl-6) -diethylthiophosphate [diazinone] and molded in the same manner to obtain a flat plate.

Hereinafter, the same evaluation was performed.

The results are shown in Table-1.

Comparative Example 4 In Example 3, 3-phenoxybenzyl 2- (4-
Ethoxyphenyl) -2-methylpropyl ether 0,
0-dimethyl 0- (3-methyl-4-nitrophenyl)
A flat plate was obtained by replacing the phosphorothioate [fenitrothion] with the same molding.

Hereinafter, the same evaluation was performed.

The results are shown in Table-1.

Comparative Example 5 In Example 3, 3-phenoxybenzyl 2- (4-
Ethoxyphenyl) -2-methylpropyl ether
-Isopropoxyphenyl N-methyl carbamate [propoxer] was replaced by the same molding, and a flat plate was obtained.

Hereinafter, the same evaluation was performed.

The results are shown in Table-1.

Comparative Example 6 100 parts by weight of vinyl chloride resin (polymerization degree 1350), 6 parts by weight of Mg / Zn heat stabilizer, 45 parts by weight of dioctyl adipate and 3-phenoxybenzyl 2- (4-ethoxyphenyl) -2-
1 part by weight of methyl propyl ether was added, and the mixture was mixed with a Henschel mixer and pelletized with an extruder to form a 160 mm × 16 mm × 2 mm flat plate using an injection molding machine.

Hereinafter, the same evaluation was performed.

The results are shown in Table-1.

Comparative Example 7 Polystyrene (manufactured by Mitsui Toatsu Chemicals, Inc .: Topolex)
550-01) 100 parts by weight of powder, 2,6-di-t-butyl-
0.05 part by weight of p-cresol, 0.1 part by weight of pentaerythyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 0.2 part by weight of glycerin monostearate, bis- (2- 1 part by weight of 3-phenoxybenzyl 2- (4-ethoxyphenyl) -2-methylpropyl ether was added to 0.1 part by weight of hydroxyltaloamine) and 0.1 part by weight of stearyl alcohol,
A mixture of a Henschel mixer was pelletized with a normal extruder, and a 160 mm × 160 mm × 2 mm flat plate was formed at an injection molding temperature of about 220 ° C. using an injection molding machine.

Hereinafter, the same evaluation was performed.

The results are shown in Table-1.

Study on sustainability Polypropylene plate containing each additive shown in Examples 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and Comparative Examples 1, 2, 3, 4, 5, The flat plates obtained in Nos. 6 and 7 were allowed to stand in a thermostatic chamber at 25 ° C. for a long time (2 months, 4 months, 6 months), and the German cockroach male adults were contacted with each standing period for 48 hours. The number of rollovers 48 hours after contact was investigated, and the percentage of rollovers was calculated. For comparison, a polypropylene plate without additives was used. The results are shown in Table-2.

In addition, the used 3-phenoxybenzyl 2- (4-ethoxyphenyl) -2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2- (4-ethoxyphenyl) -2-methylpropyl ether, 1- (3 -Phenoxyphenyl) -4- (4-ethoxyphenyl) -4
-Methylpentane and 1- (3-phenoxy-4-fluorophenyl) -4- (4-ethoxyphenyl) -4
-Methylpentane is described in JP-A-58-32840 and 58-118533.
No. 58-201737, and was synthesized according to the method described therein.

From the above results, it is clear that the polyolefin resin composition of the present invention has excellent insect repellent properties.

Claims (1)

[Claims] 1. A compound represented by the general formula (I) with respect to 100 parts by weight of a polyolefin resin. (In the formula, X represents an oxygen atom or —CH ₂ —, Y represents a hydrogen atom or a fluorine atom.) A polyolefin resin composition comprising 0.0001 to 10 parts by weight of an organic compound represented by the formula: