KR100605352B1 - Manufacturing method of antiinsect film using porous inorganic material - Google Patents

Abstract

The present invention relates to a method for preparing a insect repellent film by supporting the insect repellent in a porous inorganic material to make a insect repellent masterbatch, and dry-mixing the polyolefin powder resin with a polyolefin powder resin to form a film. The present invention relates to a method for manufacturing a master batch by supporting a polyolefin powder resin and a dry mixed insect repellent film. The method relates to a method for producing a polyolefin powder resin and a dry mixed insect repellent film. It is characterized by the fact that the film can maintain the insect repellent effect for a long time.

Description

Manufacturing method of insect repellent film using porous inorganic material {MANUFACTURING METHOD OF ANTIINSECT FILM USING POROUS INORGANIC MATERIAL}

The present invention relates to a method for producing a polyolefin-based insect repellent film having an effect on the control of pests, such as superspidities, diopterans, stamens or flies, mosquitoes that live in the ground. More particularly, the present invention relates to a method of preparing a insect repellent master batch by supporting a volatile insect repellent in a porous inorganic material at low temperature, and dry mixing it with a polyolefin powder resin to produce an insect repellent film. The present invention relates to a method for manufacturing an insect repellent film, in which an insect repellent is supported and dispersed in a film, thereby suppressing the speed of film transfer of the insect repellent to maintain the insect repellent effect for a long time.

When insect repellents, which are effective for controlling insects such as insects, insects, flies, and mosquitoes in the ground, are applied to polyolefin-based films, 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 effect is short-lived as the insect repellent transfers to the surface immediately after film forming. Of course, among the known techniques for proper dispersion of the insect repellent is a method of forming a insect repellent masterbatch using a porous plastic pellets, and dry mixed with a resin to form a film. In this case, there is no problem in the dispersion of the insect repellent, but since the base resin of the master batch is plastic, it is melted and dispersed during film forming, so there is no effect in delaying the dissolution of the insect repellent onto the film surface.

On the other hand, in the insect repellent film, an adhesive may be used so that the film may maintain the insect repellent effect for a long time by delaying the surface migration speed of the insect repellent as much as possible. In US Pat. No. 4,666,706, polyoxazoline was used as an adhesive. In the manufacturing method, the insect repellent masterbatch was prepared by melt-mixing resin, insect repellent and pressure-sensitive adhesive in a mixer, and then dry-mixing the resin with resin during film molding to prepare a insect repellent film. This method has a very good effect in terms of persistence of insect repellent effect. However, it is pointed out that the insecticide caused by decomposition and scattering of the insect repellent is a problem as the insect repellent undergoes high temperature thermal history several times until the film is manufactured. In particular, when manufacturing and using a high concentration masterbatch, there is a difficulty in wearing and wearing a gas mask due to the strong smell.

An object of the present invention is to improve the problems as described above, to effectively prevent the odor induced by the scattering of the volatile insect repellent and insect repellent effect, and to provide a method for producing a insect repellent film that can maintain the insect repellent effect for a long time.

The production method of the insect repellent film of the present invention is characterized by using a masterbatch in which a volatile insect repellent is supported on a porous inorganic material at low temperature, and the intermediate compound is dry mixed with a polyolefin powder resin to produce a insect repellent film.

In the insect repellent master batch provided by the present invention by supporting the insect repellent in a porous inorganic inorganic material at a lower temperature than the boiling point of the insect repellent, the insect repellent in the manufacturing process compared to the general method for manufacturing a master batch at a high temperature in a half-barrier mixer It is possible to reduce the unpleasant odor and content reduction caused by decomposition or scattering. Therefore, economic and stability can be secured by using this method.

Porous inorganic material used to prepare the insect repellent masterbatch provided in the present invention can be used as long as there are pores and irregularities on the surface, but the particle size is about 1 ~ 30㎛ Is suitable.

If the particle size is less than 1㎛, it may be blown into the air during the movement or work process.If the particle exceeds 30㎛, it may cause fisheye or tear of the film when forming the film. The size of is suitable. Specific examples of the porous inorganic material include zeolite, porous silica and the like.

Insect repellent to be supported in the present invention can be used any kind of insect repellent known to be effective by direct spraying method, in the present invention can be used for fruit and vegetables (Chlorpyrifos, Cas No: 2921-88-2 , Molecular weight: 350.6) and permisrin (Permethrin, Cas No .: 52645-53-1, molecular weight: 391.3), which are known to be effective in controlling pests such as flies and mosquitoes. When the same high toxicity and high volatile compounds are used, the effect is great.

In the present invention, the content of the insect repellent supported on the porous inorganic material may be up to 0.1 to 50% by weight, most preferably 5 to 30% by weight. When the amount of the insect repellent supported is less than 0.1% by weight, the content of the insect repellent masterbatch should be increased during film molding. In this case, fish or pinholes may be generated due to the increase of the inorganic content in the film. If the content exceeds 50% by weight, the effect of supporting the porous inorganic material is lowered. Therefore, the effect of preventing the occurrence of odor is less at the higher concentration.

Insect repellent master batch provided in the present invention is prepared by a solution supporting method at a low temperature.

Specifically, the production method of the insect repellent masterbatch provided in the present invention is first made by a method of completely dissolving the insect repellent in the solvent to support the solution in a porous inorganic material and then remove the solvent after standing for a certain 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.

In the case of insect repellents such as chloropyriphosph and permisrin used in the present invention, acetone, diethyl ether, hexane and the like are suitable as solvents.

The apparatus for producing the masterbatch can be any type of reactor with a stirrer, but preferably can be maintained at room temperature up to 100 ° C., and can be vacuum dried or a rotary evaporate. 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. You can add a porous inorganic substance to it and stir it. 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 inorganic 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 included in the insect repellent masterbatch can be analyzed by gas chromatography. However, when the amount of the residual solvent is large, it is preferable to increase the drying time.

Insect repellent masterbatch produced by the above method has the advantage that it is less odor than the masterbatch made by using a half-barrier mixer, and the surface of the insect repellent is very easy to handle because there is little dissolution of the insect repellent.

Insect repellent film is produced by mixing the insect repellent masterbatch prepared in the above-described process with polyolefin powder resin in an amount of 1 to 20% by weight to form a film through a film molding machine.

In order to add less than 1% by weight of the masterbatch, the amount of the insecticide supported on the inorganic material should be prepared at a high concentration (more than 50% by weight) when manufacturing the masterbatch. If the masterbatch content exceeds 20% by weight, unlike the case of using a masterbatch in which the inorganic material is highly concentrated in the resin, this process is performed by dry mixing the inorganic material with the powder resin to form a film immediately. As a result, the dispersion of the master batch may be caused, and the film surface state may deteriorate due to the occurrence of fisheye or pinhole during film forming.

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.

Example

Selection of porous minerals :

As a porous inorganic material for preparing the insect repellent masterbatch, Zeolite X type of Cosmo Materials was used. Since the structure is porous and the uneven structure is present on the surface, a large amount of insect repellent can be supported.

Preparation of the insect repellent masterbatch (5% by weight chloropyriphos) :

A glass rotary stirrer was used as an experimental instrument for supporting. The supporting method is as follows.

In a 1 L flask, 5 g of chloropyriphos (National Pharmaceutical) was dissolved in 500 ml of acetone. Zeolite (Zeolite) X Type 95g was put therein, mounted on a rotary concentrator, and slowly turned for 30 to 60 minutes under normal pressure and room temperature. 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 dried for 4 to 8 hours. The residual acetone in 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 4.5 wt% after extraction with methylene chloride and analyzed by gas chromatography.

Preparation of Insect Repellent Film (0.1 wt% Chloropyriphos) :

The insecticide masterbatch prepared above was dry mixed in a linear low density polyethylene (LLDPE) powder (4220F powder, Samsung Synthetic Chemical) at 2.0% by weight to prepare a film in a 70mm inflation film molding machine. At this time, the working conditions were film width 2.0 and thickness 40㎛, the temperature was 200 ℃ based on the extrusion die.

In the film forming process, the degree of odor generated by bubble stability and insect repellent scattering was observed (smell), and the content of the insect repellent supported in the film was measured immediately after the film molding (gas chromatography method), and it was molded to evaluate the persistence of the insect repellent effect. After leaving the film outdoors, the content of the insect repellent remaining in the film was measured at 1 week intervals (gas chromatography). The measurement results are shown in Table 1.

Comparative Example 1

Preparation of the insect repellent masterbatch (5 wt% chloropyriphos):

95% by weight of LLDPE (4220F, Samsung Synthetic Chemical) is added to a half-barrier with 5% by weight of insect repellent and started to stir at 110 ° C, melted and mixed until the melting temperature reaches 150 ° C, and then pulverized and pelletized. Insect repellent masterbatches were prepared. At this time, the pelletization process was used a single screw screw extruder, the working temperature was 200 ℃. The insect repellent content of the insect repellent masterbatch thus prepared was extracted with methylene chloride and analyzed by gas chromatography, and found to be 3.0 wt%.

Preparation of the insect repellent film (0.1 wt% chloropyriphos ) :

Insect repellent film was prepared in the same manner as in Example using the insect repellent masterbatch prepared above. Evaluation items are the same as in Example 1 and the results are shown in Table 1.

Comparative Example 2

Selection of Resin Foam :

As the LLDPE foam used to prepare the insect repellent masterbatch, Azoural MP300 from Azo-Novel was used. This foam has a non-crosslinked open cell network structure to support a large amount of insect repellent, and because it is a pellet type, it can be used by dry mixing with resin immediately after film production after master batch production. In particular, since the thermal history can be minimized until the film forming process, there is less odor generated by the decomposition or scattering of the insect repellent, and there is an advantage in that the correct amount of the insect repellent is injected into the film.

Preparation of the insect repellent masterbatch (5 wt% chloropyriphos):

The method of supporting the insect repellent body in the selected LLDPE blowing agent is the same as that of Example 1. The insect repellent content of the insect repellent masterbatch thus prepared was extracted with methylene chloride and analyzed by gas chromatography, and found to be 4.6 wt%.

Preparation of the insect repellent film (0.1 wt% chloropyriphos ) :

Insect repellent film was prepared in the same manner as in Example using the insect repellent masterbatch prepared above. Evaluation items are the same as in Example 1 and the results are shown in Table 1.

Table 1

division Odor generation (bubble stability) Insect repellent residue immediately after film forming Residual insecticides after outdoor standing 1 week 2 weeks 3 weeks 4 Weeks Example Low (stable) 0.088% by weight 0.080% by weight 0.055% by weight 0.035% by weight 0.005% by weight Comparative Example 1 Many (stable) 0.041% by weight 0 0 0 0 Comparative Example 2 Low (stable) 0.091% by weight 0 0 0 0

As can be seen from the above, the insect repellent film prepared by the present invention has no odor when the insect repellent masterbatch is produced, the produced master batch can be stored for a long time, the odor is generated even when forming the film, the film of the insect repellent Dispersion is excellent, and can carry an accurate amount of insect repellent without scattering or decomposition, and has the effect of maintaining the insect repellent effect of the film for a long time by inhibiting the speed of the film surface migration of the insect repellent.

Claims (4)

A method of manufacturing a insect repellent film, characterized in that the film is formed by dry mixing a masterbatch in which a porous inorganic material is supported at a temperature below the vaporization point of the insect repellent with a polyolefin powder resin. The method of claim 1, wherein the insect repellent is chlorpyriphos, permisrin, wood vinegar or tar, and the porous inorganic material is zeolite or porous silica. The method of claim 1, wherein the content of the volatile insect repellent supported on the porous inorganic material is 0.1 to 50% by weight based on the total weight of the masterbatch. The method of claim 1, wherein the master batch is dry mixed with the polyolefin powder resin in an amount of 1 to 20% by weight.