KR20010094304A - A resin composition for mothproof film and the mothproof film - Google Patents

Abstract

PURPOSE: A resin composition for a protection film against insects and a protection film prepared by using the resin composition are provided, which inhibits the rapid movement of an insecticide to the surface, thereby showing the insecticidal effect for a long time, and which has the water permeability, thereby being applied to a bag for a fruit. CONSTITUTION: The resin composition comprises 100 parts by weight of a base resin consisting of 40-80 wt% of a polyolefin resin and 20-60 wt% of an inorganic filler; and 0.2-50 parts by weight of a porous material which contains 10-50 wt% of a volatile insecticide. Preferably the polyolefin resin is selected from the group consisting of low density polyethylene, linear low density polyethylene, highly low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-methacrylic acid ester, and their mixtures. In addition, the polyolefin resin has the density of 0.91-0.95 g/cm3, and the melting index of 1.0-2.5 g/10 min. The porous material is selected from the group consisting of zeolite, bentonite, a pearl, silicate, wood meal, pulp meal, cellulose-based powder, zirconium phosphate, mica, clay, diatomite, polyurethane and their mixtures. And the porous material has the size of 0.1-30 micrometers.

Description

Resin composition for insect repellent film and insect repellent film {A RESIN COMPOSITION FOR MOTHPROOF FILM AND THE MOTHPROOF FILM}

The present invention relates to a resin composition and insect repellent film for fruit paper encapsulation insect repellent film having an effect on the control of pests such as superspecies, twins, poultry or flies, mosquitoes.

More specifically, the present invention melt-mixing the insect repellent carrier supporting a volatile insect repellent in a porous material at a condition lower than the volatilization temperature of the insect repellent with a polyolefin resin, an inorganic filler to form a disc sheet and then stretched it to the insect repellent film produced It is related to the excellent persistence of insect repellent effect and moisture permeability, and is suitable for application for fruit bags.

When insect repellents that are effective in controlling insects such as superspecies, diopterans, stamens, flies, and mosquitoes in the ground are used in the polyolefin-based film, the chemicals are sprayed only where necessary. It is known as one of the effective pest control methods due to the effect and the slow release of the insect repellent in the film.

However, in general, the insect repellent is incompatible with the polyolefin resin, so it is very difficult to disperse the insect repellent in the film, and the insect repellent does not last long as the insect repellent transfers to the surface immediately after film forming.

As a means to solve the above problems, there is a method of forming a insect repellent masterbatch using porous plastic pellets for proper dispersion of the insect repellent, and dry mixing it with a resin to form a film. However, in this case, there is no problem in dispersing the insect repellent, but since the base of the master batch is plastic, it melts during film forming and dies away, so there is no effect of suppressing the transition of the insect repellent to the film surface. It was.

U. S. Patent No. 4,666, 706 discloses a method of securing the persistence of the insect repellent effect by manufacturing a repellent film using polyoxazoline as an adhesive. However, when the insect repellent film thus prepared is used for fruit bag encapsulation, the long-term retention characteristics of the insect repellent effect are excellent, but the moisture permeability is almost absent due to the dampness of the fruit.

Therefore, an object of the present invention is to improve the problems as described above, the insect repellent film composition for the insect repellent film exhibiting excellent moisture permeability as well as maintaining the insect repellent effect for a long time by suppressing the film surface migration speed of the insect repellent and the fruit bag using the same To provide a insect repellent film.

The composition of the present invention for achieving the above object is a porous containing 10 to 50% by weight of the volatile insecticide compared to the porous material with respect to 100% by weight of the base resin consisting of 40 to 80% by weight of polyolefin resin, 20 to 60% by weight of inorganic filler It is the same as the resin composition for insect repellent films, characterized by adding 0.2 to 50% by weight of the substance.

At this time, the polyolefin resin is one or more of low density polyethylene, linear low density polyethylene, ultra low density polyethylene, high density polyethylene, ethylene vinyl acetate copolymer, polypropylene, ethylene propylene copolymer, ethylene propylene diene copolymer, ethylene methacrylate ester It features.

In addition, the polyolefin resin has a density of 0.91-0.95 g / cm 3 and a melt index at 190 ° C. is 1.0-2.5 g / 10 min.

In addition, the porous material is characterized in that at least one selected from zeolite, bentonite, pearlite, silicate, wood powder, pulp powder, cellulose-based powder, zirconium phosphate, mica, cray, diatomaceous earth and polyurethane foam, the porous The material is characterized by having a particle diameter of 0.1 ~ 30㎛.

In addition, the volatile insecticides are pyrethroid-based permethrin, alletrin, pyrethrin, bioresmethrin, tetramethrin, organophosphorus dichlorboth, phenytrothion, chlorpyriphos, organochlorine DDT, gamma-HCL, Malachion, carbamate-based propoxol, PHC and natural wood vinegar is characterized in that at least one selected.

In addition, the configuration of the present invention includes an insect repellent film for fruit packaging produced using the resin composition for insect repellent film.

The insect repellent film of the present invention relates to an insect repellent film prepared by supporting a volatile insect repellent in a porous material at a low temperature lower than its volatilization temperature and then melting and mixing it with a polyolefin resin and an inorganic filler to form a disc sheet and then stretching it. Excellent durability and moisture permeability make it suitable for use in fruit bags.

In providing the insect repellent carrier used in the present invention, when the insect repellent is supported on the porous material, the insect repellent should be supported at a lower temperature than the vaporization point of the insect repellent to reduce the unpleasant odor and content reduction caused by decomposition or scattering of the insect repellent. .

The porous material used to prepare the insect repellent carrier provided in the present invention is zeolite, bentonite, pearlite (pearlite), silicate, wood powder, pulp powder, cellulose powder, zirconium phosphate, mica, clay, diatomaceous earth, polyurethane foam As long as there are pores such as a thermosetting foam such as, any one can be used, and a single species or a mixture of two or more species may be used.

In addition, the carrier is used to put into the film, the particle size of about 0.1 ~ 30㎛. If the average particle size is 0.1㎛ or less, it is difficult to disperse, if the particle exceeds 30㎛ there is a fear that the film is formed when the fish eye and the film is torn during stretching. Preferably about 1-5 micrometers is suitable.

Insect repellent to be supported in the present invention can be used any insect repellent known to be effective by direct spraying method. Specific examples include pyrethroid type permethrin, alletrin, pyrethrin, bioresmethrin, tetramethrin, organophosphorus dichlorbose, phenytrothion, chlorpyriphos, organochlorine DDT, gamma-HCL, malachion, It is a carbamate type propoxol, PHC, etc. It can also use one or two or more insecticides mixed.

In preparing the insect repellent carrier provided by the present invention, the content of the insect repellent supported on the porous material may be up to 50% by weight compared to the carrier, but it is most suitable when it is 10 to 20% by weight. Even if the content of the insect repellent supported is more than 50% by weight, the insect repellent may be further supported, but at higher concentrations, the insect repellent may coat the carrier, thereby reducing the effect of using the porous material as the carrier.

The insect support carrier provided in the present invention is prepared by a solution supporting method at a low temperature. Specifically, the method for preparing the insect repellent carrier provided in the present invention is performed by first removing the solvent after leaving the solution in which the insect repellent is completely dissolved in the solvent in a porous material and then leaving it for a predetermined time. At this time, the solvent used should have a high volatility, lower vaporization temperature than the insect repellent, solubility in the insect repellent is so large that it must be able to dissolve the insect repellent completely.

As a solvent for dissolving the insect repellent used in the present invention, acetone, dimethyl ether (Ether), hexane (Hexane) and the like are suitable.

The apparatus for preparing the carrier can be any kind of reactor equipped with a stirrer, but preferably can maintain a temperature of up to 100 ℃ at room temperature, a vacuum drying reactor or a rotary evaporator (rotary evaporator) It is suitable to use. First, a certain amount of solvent and insect repellent is put into the reactor and the insect repellent is completely dissolved. The porous material is added and stirred here. The amount of the preferred solvent is suitably a little larger in volume than the porous inorganic material used. Slowly stir until the insect repellent enters the porous material. The stirring time is preferably 30 to 60 minutes. When removing the solvent after stirring, it is advantageous to volatilize for a long time by a vacuum drying method at a low temperature so that even the solvent contained in the carrier can be completely removed. The amount of the residual solvent and the amount of the insect repellent contained in the insect repellent carrier thus made can be analyzed by gas chromatography. However, when the amount of the residual solvent is large, it is preferable to increase the drying time.

In preparing the insect repellent film with the insect repellent carrier prepared by the above method, the content of the insect repellent is 0.1 to 5 parts by weight relative to the composition consisting of the olefin resin and the inorganic filler.

When the content of the insect repellent is less than 0.1 parts by weight, the insect repellent effect is insignificant. When the content of the insect repellent exceeds 5 parts by weight, the insect repellent effect is excellent when applied as an fruit bag, but the insect repellent may remain on the skin because it does not exceed 5 parts by weight. It is good.

In the present invention, the composition ratio of the polyolefin resin and the inorganic filler constituting the base resin is 40 to 80% by weight of polyolefin resin, preferably 55 to 70% by weight, 20 to 60% by weight of inorganic filler, preferably It is the range of 50-30 weight%. If the inorganic filler is less than 20% by weight, there is a defect in that air is not continuously penetrated through the vent due to peeling between the polyolefin resin and the inorganic filler, which impairs breathability.If the inorganic filler exceeds 60% by weight, the film breaks or is stretched. Elongation is likely to drop in terms of physical properties.

The polyolefin resin in the present invention is a polyolefin-based thermoplastic resin comprising a homopolymer of ethylene or propylene or a copolymer of ethylene or propylene with another comonomer (a compound having 4 or more carbon atoms and having at least one double bond in the molecule), eg For example, low density polyethylene, linear low density polyethylene, ultra low density polyethylene, high density polyethylene, ethylene vinyl acetate copolymer, polypropylene, ethylene propylene copolymer, ethylene propylene diene copolymer, ethylene methacrylic acid ester or any of these mixtures may be used. Preferably, the density is 0.91-0.95 g / cm 3, and the melt index is 1.0-2.5 g / 10 min (at 190 ° C.).

The linear low density polyethylene is prepared by copolymerization with a Ziegler type catalyst or a metallocene catalyst as a copolymer of ethylene and other alpha olefins.

In the present invention, the inorganic filler is calcium carbonate, silica, barium sulfate, magnesium sulfate, calcium sulfate, talc, kaolin, aluminum hydroxide, magnesium hydroxide, zinc oxide, alumina, titanium oxide, mica, zeolite, diatomaceous earth, magnesium carbonate, cray or Mixtures of these are used. Forms of the inorganic fillers include plate, needle, spherical and the like, but spherical is most preferred, and the average particle diameter is in the range of 0.1 to 30 μm, preferably 1 to 3 μm. If the average particle size is less than 0.1um, the inorganic filler is difficult to disperse in the resin, and thus the mechanical properties are deteriorated. If the average particle diameter is more than 30um, the film may be broken during the stretching process of the film for ensuring breathability.

Meanwhile, the inorganic filler may be coated with stearic acid or the like to increase the dispersibility of the inorganic material in the resin.

Hereinafter will be described in detail a method for manufacturing a fruit film insect repellent film of the present invention.

The insect repellent carrier, polyolefin resin, inorganic filler, and the usual additives are adjusted in an appropriate amount, and then mixed into a conventional blender or a mixer. As the mixer, a drum, a dumbler type mixer, a ribbon blender, a Henschel mixer supermixer, or the like may be used, but a high speed stirring type mixer such as a hexyl mixer is preferable.

Next, the mixture is kneaded, which is appropriately carried out by a conventionally known apparatus such as a conventional single screw extruder, a twin screw mixer, a mixing roll, a balbaric mixer, a twin screw kneader or the like. The kneaded resin composition is then pelletized. The resin composition pellets are put into a flattener, and the film is molded according to a conventional film forming apparatus and molding method by extrusion processing. Inflation molding using a circular die and tee-die extrusion molding with a tee die are appropriately employed. You may do it.

Next, the sheet molded by the extrusion method is stretched in the traveling direction (MD) in the range of 1.2 to 6.0 times, preferably 1.5 to 5.0 times, at a temperature between the glass transition point and the melting point or less. In this case, if the temperature is lower than the glass transition point, the film cannot be stretched because the film is broken before the elongation exceeds the yield point. If the temperature exceeds the melting point, the aeration rate can be obtained by the flow of the molecular chain. It is impossible. In addition, when the draw ratio is less than 1.2 times, sufficient aeration amount is not obtained, and when the draw ratio exceeds 6 times, cutting phenomenon occurs frequently during stretching and a film cannot be stably obtained. The film stretched in the running direction is stretched in the width direction (TD) under the conditions and the draw ratio of the above temperature range to obtain a biaxially stretched insect repellent film.

Moreover, it is also possible to carry out only uniaxial stretching, without performing biaxial stretching as mentioned above. That is, the production method of the insect repellent film according to the present invention can be produced by either uniaxial or biaxial stretching, it is preferable to stretch so that the total area stretching ratio is in the range of 1.5 to 36 times. If the area stretching ratio is less than 1.5 times, sufficient moisture permeability cannot be obtained. If the area stretching ratio is more than 36 times, moisture permeability is obtained, but there is a fear that the film breaks during the stretching process. In order to improve the dimensional stability, the film after extending | stretching may heat-fix.

The physical properties of the breathable insect repellent film impregnated with the insect repellent prepared in accordance with the present invention freely depending on the type and physical properties of the polyolefin resin, the type and particle size of the inorganic filler and the mixing ratio, stretching temperature, stretching ratio, stretching method and the like between them. It is adjustable.

The present invention can be understood in more detail through the following examples and comparative examples, the following examples and comparative examples are not intended to limit the scope of the present invention but are described for illustrative purposes.

Production Example

Selection of porous minerals:

As a porous inorganic material for preparing the insect repellent masterbatch, Zeolite X type of Cosmo Materials was used. Because of its porous structure and uneven structure on the surface, it can support a large amount of insect repellent.

Preparation of the insect repellent carrier (20% by weight permethrin):

A glass rotary stirrer was used as an experimental instrument for supporting. The supporting method is as follows. 20 g of chloropyriphos (National Pharmaceutical Co., Ltd.) was added to a 1 L flask and 500 ml of acetone was added to dissolve it. 80 g of zeolite X type was added thereto, mounted on a rotary concentrator, and slowly rotated under normal pressure and normal temperature for 30 to 60 minutes. After the acetone solution was supported on the porous inorganic material, the temperature of the rotary concentrator was raised to 40 to 80 ° C., and vacuum was dried for 4 to 8 hours. The residual acetone inside the porous inorganic material became 0.5% by weight or less. Acetone evaporated in a rotary concentrator is used as a solvent for the next preparation. The content of chloropyriphos contained in the insect repellent masterbatch was 18.5% by weight after analysis with gas chromatography after extraction with methylene chloride.

(Example 1)

Insect repellent carrier was used for the base resin composition composed of 30 wt% of linear low density polyethylene A (Samsung General Chemical 6220F), 30 wt% of linear low density polyethylene B (Hyundai Petrochemical ST408), and 40 wt% of calcium carbonate (OMYA OMYACARB 2). 2.5 parts by weight of primary, secondary antioxidants, processing aids (3M FX5924), dispersant (Songwon, Zn-st) and the like were mixed in a Henschel mixer, and the mixture was kneaded with a twin screw kneader and pelletized. The obtained resin composition pellets were introduced into a film forming extruder through a hopper and melt-extruded at 220 ° C. to prepare a melt as a disc sheet through a T-die. The obtained original sheet was stretched 1.7 times in the running direction (MD) at a stretching temperature of 60 ° C., stretched 1.5 times in the width direction (TD) while maintaining the tenter temperature at 120 ° C., and finally stretched by heat treatment at 110 ° C. for 1 day. An insect repellent film for fruit bags having a thickness of 38 μm processed at an area ratio of 2.6 was prepared.

After the prepared film was left to stand outdoors, the content of the insect repellent remaining in the film was measured at a weekly interval (gas chromatography). The measurement results are shown in Table 1.

(Comparative Example 1)

In the case of adding the insect repellent in Example 1 was carried out in the same manner as in Example 1 except that directly added without using a porous carrier and the amount of added calcium carbonate was replaced by linear low density polyethylene A. The residual amount measurement result in the film is shown in Table 1.

(Examples 2-4, Comparative Example 2)

A film was prepared in the same manner as in Example 1 with the composition of Table 2. The moisture permeability and insect repellent (insecticide to mosquitoes) were evaluated for the produced film. The evaluation results are shown in Table 2.

Breathability evaluation

The moisture permeability evaluation of the film was conducted in accordance with KS A 1013. Since there is no requirement for moisture permeability, the spec. Of breathable film that is commonly applied is set as a target value, and the value is from 3,000 to 10,000 g / 24hr㎡. to be.

Insecticidal test for mosquitoes

With the breathable film before and after the insect repellent being placed on the test bench, place a 15cm x 15cm x 3cm acrylic box, spit 50 Clux pipiens pallens adults, and contact them for 30 minutes. The mortality was checked 24 hours later.

As described above, the resin composition for insect repellent films of the present invention and the fruit film repellent insect repellent film prepared by the composition has a remarkable effect of gradually releasing the insect repellent to sustain the drug efficacy.

In addition, the insect repellent film composition of the present invention and the insect repellent film for fruit packaging made from the composition have a remarkable insecticidal effect as compared to a film containing no insect repellent carrier carrying an insect repellent.

Further, the resin composition for insect repellent films of the present invention and the insect repellent insect repellent film prepared by the composition have a similar or superior moisture permeability as compared with a film that does not contain the insect repellent carrier.

Claims (7)

It is composed by adding 0.2 to 50% by weight of the porous material containing 10 to 50% by weight of the volatile insecticide relative to the porous material with respect to 100% by weight of the base resin consisting of 40 to 80% by weight of the polyolefin resin, 20 to 60% by weight of the inorganic filler Resin for insect repellent film, characterized in that. The method of claim 1, wherein the polyolefin resin is a low density polyethylene, linear low density polyethylene, ultra low density polyethylene, high density polyethylene, ethylene vinyl acetate copolymer, polypropylene, ethylene propylene copolymer, ethylene propylene diene copolymer, ethylene methacrylic acid ester 1 or more types of resin composition for insecticide films characterized by the above-mentioned. The resin composition for insect repellent films according to claim 1 or 2, wherein the polyolefin resin has a density of 0.91 to 0.95 g / cm 3 and a melt index of 1.0 to 2.5 g / 10 min at 190 ° C. The method of claim 1, wherein the porous material is zeolite, bentonite, pearlite, silicate, wood powder, pulp powder, cellulose-based powder, zirconium phosphate, mica, cray, diatomaceous earth and polyurethane foam, characterized in that at least one selected from Insect repellent film resin composition. The resin composition for insect repellent films according to claim 1 or 4, wherein the porous material has a particle diameter of 0.1 to 30 µm. According to claim 1, wherein the volatile insect repellent is pyrethroid permethrin, alletrin, pyrethrin, bioresmethrin, tetramethrin, organophosphorus dichlorbose, phenytrothion, chlorpyriphos, organochlorine DDT, Resin composition for insect repellent film, characterized in that at least one selected from gamma-HCL, malachion, carbamate-based propoxol, PHC and natural wood vinegar. Insect repellent film, characterized in that prepared using the resin composition for insect repellent film of any one of claims 1 to 6.