JP2002029904A - Method for producing insect-proofing film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an insect-proofing film by melt- mixing a polyolefin resin and an inorganic filler, with an encapsulated insect- proofing agent. SOLUTION: This method for producing the insect-proofing film is characterized by melt-mixing 0.01-10 pts.wt. capsules including the insect-proofing agent with 20-80 pts.wt. polyolefin resin, and 20-80 pts.wt. inorganic filler, forming the melt-mixed product into a raw sheet by an inflation method or a T-die casting method, and monoaxially or biaxially orienting the resultant raw sheet so that the total area draw ratio may be 1.5-36 times according to the required moisture permeability. The film produced by the method can maintain the insect-proofing effects for a long time by suppressing the rapid migration of the insect-proofing agent to the surface of the film, has moisture permeability, and is especially suitable for a bag for a fruit tree.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyolefin-based insect repellent film which is effective for controlling pests such as Coleoptera, Diptera, Lepidoptera or flies and mosquitoes living in the ground. More specifically, the present invention relates to a method for producing an insect repellent film by melt-mixing an encapsulated insect repellent with a polyolefin resin and an inorganic filler, and the film thus produced has excellent persistence of the insect repellent effect. It has moisture permeability and is particularly suitable for application to fruit tree bags.

[0002]

BACKGROUND OF THE INVENTION Coleoptera, diptera or flies living in the ground,
The method of using insect repellents that are effective in controlling pests such as mosquitoes into polyolefin-based films is more effective than spraying insect repellents directly onto the polyolefin film. It is known as one of the effective pest control methods due to the property that the insect repellent contained therein is gradually released. However, in general, since the insect repellent is not compatible with the polyolefin resin, it is very difficult to disperse the insect repellent in the film. There is. Of course, among known techniques for appropriately dispersing the insect repellent, there is a method of forming an insect repellent masterbatch using porous plastic pellets and dry-mixing this with a resin to form a film.

[0003] In this case, there is no problem in dispersing the insect repellent, but since the base of the masterbatch is made of plastic, it is melted and loses its shape at the time of forming the film. Insect repellent effect is short-lived.

In US Pat. No. 4,666,706, an insect repellent film is manufactured using polyoxazoline as an adhesive to ensure the persistence of the insect repellent effect. However, when the insect repellent film thus produced is applied to a fruit tree bag, there is a problem that although the insect repellent effect is maintained for a long time, the fruit is soaked due to moisture damage due to little moisture permeability. did.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned problems, and it is an object of the present invention to suppress the transfer rate of the insect repellent to the film surface and maintain the insect repellent effect for a long period of time. Another object of the present invention is to provide a method for producing a film, which can secure moisture permeability of the film and is particularly suitable for application to fruit tree bags.

[0006]

According to the method for producing an insect repellent film of the present invention, an insect repellent film is prepared by melt-mixing an encapsulated insect repellent with a polyolefin resin and an inorganic filler, producing an original plate and a resin sheet, and then stretching the resultant. It is related to the manufacturing method, has excellent persistence of insect repellent effect, has moisture permeability,
Particularly suitable for use in fruit tree bags.

The present invention relates to a polyolefin resin of 20 to 80.
After melt-mixing 0.01 to 10 parts by weight of a capsule containing an insect repellent with 20 to 80 parts by weight of an inorganic filler, an original sheet is manufactured by an inflation or tea-die casting method. In accordance with the required moisture permeability, the film is stretched in a total area of 1.5 to 36%.
The present invention relates to a method for producing an insect repellent film, characterized in that the film is stretched uniaxially or biaxially so as to be twice as large.

The insect repellent capsule used in the present invention is used for ensuring the persistence of the insect repellent effect. The capsule material may be cellulose derivative, gelatin resin, starch, polyamide, polyester, polycarbonate, polyurethane or polyurea. (Urea) It is produced by an emulsion polymerization or a supporting method using one or more of the polymers. The particle size of the capsule can be about 0.1 μm to 30 μm.

When the size of the capsule is 0.1 μm or less, it is very difficult to manufacture the capsule. When the size is 30 μm or more, the surface condition of the film such as pinholes may be deteriorated at the time of film formation.

[0010] The insect repellent filled in the capsule is
Any insect repellent which is known to be effective by the method of direct spraying can be used. Specific examples include pyrethroid-based famethrin,
Arethrin, pyrethrin, bioresmethrin, tetramethrin, organic dichlorobos, fenitrothion, chloropyripos, organochlorine DDT, gamma-H
CL, malathion, covermate propoxur, PHC, and the like, and one or more insect repellents can be used in combination.

The content of the added insect repellent is 0.01 to 10 parts by weight based on the resin composition. When the content is less than 0.01 part by weight, an insect repellent effect is obtained. When the amount exceeds 10 parts by weight, the insect repellent effect is excellent, but it is difficult to handle due to the generation of odor when manufacturing or applying the film, and the price competitiveness is lowered due to an increase in manufacturing cost. Sometimes.

The resin composition used in the present invention comprises a polyolefin resin and an inorganic filler. The content of the inorganic filler is from 20 to 80 parts by weight based on 80 to 20 parts by weight of the polyolefin resin. More preferably 30
Used at 60 to 60 parts by weight. Content of inorganic filler is 2
If the amount is less than 0 parts by weight, it is difficult to obtain a desired moisture permeability during film forming, and if the content is 80 parts by weight or more, the extrudability of the film forming is significantly reduced.

The film can be formed by an inflation or casting method, and in order to ensure high moisture permeability, the original sheet produced by an extruder is stretched uniaxially or biaxially to secure the required moisture permeability.

In the present invention, the polyolefin resin is a homopolymer of ethylene or propylene, or a comonomer different from ethylene or propylene (having a carbon number of 4).
Compounds having at least one double bond in the molecule above) is a polyolefin-based thermoplastic resin comprising a copolymer, for example, low-density polyethylene, linear low-density polyethylene, very low-density polyethylene, high-density polyethylene, Ethylene vinyl acetate copolymer, polypropylene, ethylene propylene, ethylene propylene diene copolymer, ethylene methacrylate or a mixture thereof can be used.

The polyolefin resin desirably has a density of 0.91 to 0.95 g / cm ³ and a melting index of 0.5.
It is good to be 2.0 g / 10 minutes (190 ° C.).

The linear low-density polyethylene is produced by copolymerizing a copolymer of ethylene and another alpha olefin with a Ziegler catalyst or a metallocene catalyst.

In the present invention, the inorganic filler includes calcium carbonate, silica, barium sulfate, magnesium sulfate, calcium sulfate, talc, kaolinite, aluminum hydroxide, magnesium hydroxide, zinc oxide, alumina, titanium oxide, mica, zeolite, Diatomaceous earth, magnesium carbonate, clay or mixtures thereof are used. Examples of the form of the inorganic filler include a plate shape, a needle shape, and a spherical shape, and a spherical shape is most desirable, and the average particle size is 0.1 to 10 μm.
Preferably it is in the range of 0.1 to 3 μm. When the average particle size is less than 0.1 μm, it is difficult to disperse the inorganic filler in the resin, and the mechanical properties are deteriorated.
If the thickness exceeds μm, the surface may be defective due to generation of pinholes or holes in the film.

On the other hand, the inorganic filler coated with stearic acid or the like may be used in order to enhance the dispersibility of the inorganic substance in the resin.

Hereinafter, the method for producing an insect repellent film for fruit tree bags according to the present invention will be described in more detail.

The insect-controlling capsule, the polyolefin resin, the inorganic filler and the usual additives are adjusted in appropriate amounts, and put into a usual blender or a mixer to mix. As the mixer, a drum, a tumbler type mixer, a ribbon blender, a Hensel mixer, a super mixer or the like can be used, but a high-speed stirring type mixer such as a Hensel mixer is preferable.

Next, the mixture is kneaded appropriately by a conventionally known device, for example, a usual single screw extruder, a twin screw mixer, a mixing roll, a Banbury mixer, a twin screw kneader or the like. Is done. continue,
The kneaded resin composition is pelletized. The resin composition pellets are put into a hopper, and a film is formed in accordance with a normal film forming apparatus and a forming method by extrusion, but the inflation molding by a circular die, the tea die extrusion by a tea die, and the like are appropriately adopted. It should be implemented.

The film forming method can be made different depending on the required moisture permeability. However, when the film is used for low moisture permeability (for example, for the surface bag of a pear double bag, the moisture permeability is 1000 g / 24 hr, m ² or less), if formed by a general film forming method, the thickness of the film is adjusted to a level of 15 to 50 μm to obtain about 1000 μm.
The moisture permeability can be adjusted to about g / 24 hr, m ² .

However, in the case of high moisture permeability (as a practical example,
For pear double bag surface bag, moisture permeability 2000 to 10,000g
/ 24 hr, m ² ), a sheet formed based on the extrusion method is heated at a temperature between the glass transition point and the melting point of 1.2 to 1.2.
The film is stretched in the running direction (MD) in a range of 6.0 times, preferably in a range of 1.5 to 5.0 times. In this case, when the temperature is lower than the glass transition point, the film is ruptured before the elongation exceeds the yield point and cannot be stretched. Due to the flow of the chains, it is not possible to obtain a ventilation volume during stretching in the running direction.

On the other hand, if the stretching ratio is less than 1.2 times, a sufficient amount of air cannot be obtained, and if the stretching ratio exceeds 6 times, a cutting phenomenon frequently occurs during stretching, resulting in a stable Can not get the film. Subsequently, the film stretched in the running direction is stretched in the width direction (TD) under the conditions of the above temperature range and the stretching ratio, to obtain a biaxially stretched insect repellent film.

Further, it is also possible to perform only uniaxial stretching without performing biaxial stretching as described above. That is, the method for producing an insect repellent film for high moisture permeability according to the present invention can be produced by either uniaxial or biaxial stretching, and is stretched so that the total area stretching ratio is in the range of 1.5 to 36 times. It is desirable to do. If the area stretching ratio is less than 1.5 times, sufficient moisture permeability cannot be obtained, and if it exceeds 36 times, moisture permeability can be obtained, but the film may be broken during the stretching process. The stretched film may be heat-set in order to improve its dimensional safety.

The physical properties of the film containing the insecticide prepared according to the present invention include the type and physical properties of the polyolefin resin, the type and particle size of the inorganic filler, the mixing ratio between them, the molding method, and the stretching temperature. It can be freely adjusted depending on conditions such as stretching ratio, stretching method and the like.

The above and other objects, features and advantages of the present invention will be apparent from the following description of preferred embodiments of the present invention with reference to the accompanying drawings.

[0028]

The present invention can be understood more specifically through the following examples and comparative examples. The following examples and comparative examples are not intended to limit the scope of the present invention. Rather, they are provided for illustrative purposes.

Example 1 20 parts by weight of linear low-density polyethylene A (Samsung Sogo Chemical 6220F), 30 parts by weight of linear low-density polyethylene B (SK FT), and calcium carbonate (OMYA OMY)
ACARB 2) 50 parts by weight of the base resin composition, 10 parts by weight of the encapsulated insect repellent (100% by weight of the whole insect repellent capsule, the content of famesulin as an insect repellent was 81% by weight, The primary and secondary antioxidants, processing preparation (3M FX5924), dispersant (Matsubara Sangyo, Zn-st), UV stabilizer, etc. are mixed with a Hensel mixer, and this mixture is mixed with a twin-screw kneader. After kneading, the mixture was pelletized.

The obtained resin composition pellets were put into a film forming extruder through a hopper, melt-extruded at 220 ° C., and this melt was produced as a base sheet through a tea die. The obtained original sheet is stretched 1.7 times in the running direction (MD) at a stretching temperature of 60 ° C., and the tenter temperature is set to 120.
Stretched 1.5 times in the width direction (TD) while maintaining at
Heat treatment was performed at 110 ° C. for 1 day to finally produce a 38 μm-thick insect repellent film processed to a stretch area ratio of 2.6.

After leaving the produced film outdoors,
The content of the insect repellent remaining in the film was measured at intervals of 3 weeks (high pressure liquid chromatography). The measurement results are shown in Table 1.

Example 2 and Comparative Example 2 Films were produced using the compositions shown in Table 2 in the same manner as in Example 1. The produced film was evaluated for moisture permeability and insect repellency (insecticidal activity against the worm). The evaluation results are shown in Table 2.

* Evaluation of moisture permeability The evaluation of moisture permeability of the film was conducted based on KS AIO13.
To the required specifications for moisture permeability.
Because of the lack of
Set to. For pear bags, the surface bag is 100-1,000
g / 24 hrm ^Two, The middle bag has a value of 200 to 10,000
0g / 24hrm^TwoIt is.

* Insecticidal test on worms Insects A 15 cm x 15 cm x 33 cm acrylic box was placed with the breathable film before and after the insect repellent treatment laid out on the test table, and 50 worms were placed in the box. The larvae were released and kept in contact for 24 hours, then transferred to an observation box and fed to check the number of killed experimental insects.

[0035]

[Table 1]

[0036]

[Table 2]

* Insect repellent content in insect repellent capsule: 81% by weight (famethrin, cis-, trans-ratio: 4/6) The present invention has been described in detail by way of the examples. Without limitation, those skilled in the art to which the present invention pertains can modify or change the present invention without departing from the spirit and spirit of the present invention.

[0038]

The insect repellent film produced by the method of the present invention has a capacity of 1200 p.p.
pm, and the residual amount decreased to about 100 ppm after 21 weeks, indicating that the effect of gradually releasing the insect repellent was excellent, and that the moisture permeability and the insecticidal effect were also remarkable.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 57/12 A01N 57/14 E 57/16 102B 57/14 53/00 502C 57/16 102 504E (72 ) Inventor Hong Soh-gu, 108 108, 902, Sejong Apartment, Tamin-dong, Yuseong-gu, Daejeon, Republic of Korea Terms (reference) 4H011 AC01 AC06 BA01 BB02 BB13 BB15 BB17 BC18 BC19 BC20 DA05 DA07 DC05 DC10 DF03 DG16 DH02 DH04 DH05 DH06 DH10 DH11

Claims (6)

[Claims] 1 to 20 parts by weight of a polyolefin resin,
After melt-mixing 20 to 80 parts by weight of the inorganic filler and 0.01 to 10 parts by weight of the capsule containing the insect repellent, an original sheet is manufactured by an inflation or tea-die casting method, and then required. A method for producing an insect repellent film, comprising uniaxially or biaxially stretching such that the total area stretching ratio is in the range of 1.5 to 36 times depending on the moisture permeability. 2. The insect repellent is selected from the group consisting of famethrin, allethrin, pyrethrin, bioresmethrin, tetramethrin, dichlorobos, fenitrothion, chloropyripos, DDT, gamma-HCL, malathion, propoxur, PHC and grass fluid. The method for producing an insect repellent film according to claim 1, wherein the selected one or more kinds are used. 3. The capsule containing the insect repellent is at least one selected from the group consisting of cellulose derivatives, gelatin resins, starch, polyamides, polyesters, polycarbonates, polyurethanes and urea resin polymers as capsule material. The method for producing an insect repellent film according to claim 1, wherein the substance is produced by an emulsion polymerization or a supporting method using the substance. 4. The polyolefin resin is a low-density polyethylene, a linear low-density polyethylene, a very-low-density polyethylene, a high-density polyethylene, an ethylene-vinyl acetate copolymer, a polypropylene, an ethylene-propylene copolymer, an ethylene-propylene diene copolymer and 2. The method for producing an insect repellent film according to claim 1, wherein the method is at least one selected from the group consisting of ethylene methacrylates. 5. The polyolefin resin has a density of 0.5.
91 to 0.95 g / cm ³ , melting index 0.5 to 2.0
2. The method for producing an insect repellent film according to claim 1, wherein the temperature is g / 10 minutes (190 ° C.). 6. The inorganic filler includes calcium carbonate, silica, barium sulfate, magnesium sulfate, calcium sulfate, talc, kaolinite, aluminum hydroxide, magnesium hydroxide, zinc oxide, alumina, titanium oxide, mica, zeolite, 2. A diatomaceous earth, magnesium carbonate, clay, and at least one selected from the group consisting of stearic acid-coated bodies thereof.
A method for producing the insect repellent film as described above.