JP2011201967A - Master batch pellet and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide master batch pellets capable of suppressing generation of toxic gas during the production thereof and of preventing corrosion of production machines etc., and a method for producing the same.SOLUTION: The master batch pellets are obtained by blending 0.45-5 pts.mass of a fluorine-based surfactant and 4-48 pts.mass of a hydrocarbon-based surfactant with 100 pts.mass of a resin. The resin comprises a low density polyethylene-based resin and/or an ethylene-vinyl acetate copolymer resin. The hydrocarbon-based surfactant is at least one selected from the group consisting of partial esters of a polyhydric alcohol and a fatty acid and an alkylene oxide addition compound thereof.

Description

  The present invention relates to a master batch pellet and a manufacturing method thereof.

  Conventionally, there is so-called house cultivation in which crops are cultivated using a house made of a resin film as an outer wall and a metal pipe or the like as a framework. As an outer wall used in such a house, for example, a polyvinyl chloride film or the like is known, but from the viewpoint of weather resistance and heat retention of the house, a film made of a polyolefin resin (hereinafter simply referred to as a polyolefin resin film). In recent years.

  The polyolefin-based resin is a homopolymer or a copolymer such as α-olefin. Examples of polyolefin resins include low density polyethylene resins and ethylene-vinyl acetate copolymer resins. And these polyolefin resin is shape | molded by methods, such as injection molding, extrusion molding, blow molding, and inflation molding, The polyolefin resin film used as the outer wall of a house is produced.

  By the way, when performing house cultivation, if a temperature difference occurs inside and outside the house and mist is generated, water droplets are generated inside the film and light transmittance is reduced, or water droplets fall on crops and inhibit growth. There is. In other words, the polyolefin resin film that becomes the outer wall of the house is filled with the water vapor in the house when the temperature difference between the inside and outside of the house becomes large. It is desirable to have the ability to prevent water from getting wet or to prevent water droplets from condensing on the inside of the house (inside the polyolefin resin film) and dropping water droplets on the agricultural products in the house. Therefore, a certain amount of various surfactants are blended in the polyolefin resin film serving as the outer wall of the house in order to give the polyolefin resin film the performance as described above. In the following description, a polyolefin resin film that serves as an outer wall of a house is simply referred to as an agricultural film.

  As a method of blending various surfactants into the agricultural film, there is a method of blending the various surfactants directly into a polyolefin resin. On the other hand, a method of pre-manufacturing master batch pellets blended with the above various surfactants and blending the master batch pellets with a resin (polyolefin-based resin) serving as the base of the agricultural film during molding of the agricultural film It has been known. In addition, a master batch pellet may be called a master pellet and a master batch.

  In general, as a method of blending the above-mentioned various surfactants into an agricultural film, the latter method, that is, masterbatch pellets are manufactured in advance and applied to a resin (polyolefin resin) serving as the base of an agricultural film. Many methods of blending master batch pellets are used. The reason for this is that, compared with the case where the above-mentioned various surfactants are directly blended with the resin used as the base of the agricultural film, the method using the master batch pellet is more effective than the resin used as the base of the agricultural film. This is because there is an advantage that the dispersibility with the active agent is improved, and the above-mentioned various surfactants can be blended with high accuracy into the resin which is the base of the agricultural film.

  In addition, as an example of the master batch which mix | blended surfactant, there exists the technique (The master batch and the manufacturing method of the said master batch) currently disclosed by patent document 1, for example.

JP 11-335568 A

  The technique disclosed in Patent Document 1 is a master batch in which a fluorosurfactant and a basic inorganic compound are blended in a thermoplastic resin. In addition, the masterbatch currently disclosed by the said patent document 1 is called the conventional masterbatch.

  Specifically, a conventional masterbatch is blended with 1 to 70 parts by mass of a fluorine compound (fluorine surfactant) and 0.01 parts by mass of a basic inorganic compound with respect to 100 parts by mass of a thermoplastic resin. ing. Moreover, the technique currently disclosed by the said patent document 1 is the manufacturing method which mixes the said masterbatch with a mixer, knead | melts it using an extruder, and makes it pellet form.

  In general, when the fluorosurfactant is contained in a master batch pellet at a certain high ratio, when the master batch pellet is kneaded and melted, the fluorosurfactant is decomposed to produce hydrogen fluoride. Is known to occur. Therefore, the conventional masterbatch disclosed in Patent Document 1 contains a basic inorganic compound to neutralize the acid (hydrogen fluoride) generated when the masterbatch is kneaded and melted. .

  In other words, a conventional masterbatch has a fluorochemical surfactant decomposed when the masterbatch is produced, and a large amount of toxic hydrogen fluoride is generated. There was a problem of corroding.

  The present invention solves the above-mentioned problems, and provides a master batch pellet that can suppress the generation of corrosive gas during production and prevent corrosion of a production machine, and a production method thereof.

  In order to achieve the above object, the present invention has the following features. That is, the first invention is a master batch pellet containing a resin, a fluorine-based surfactant, and a hydrocarbon-based surfactant. In the master batch pellet, 0.45 to 5 parts by mass of a fluorosurfactant and 4 to 48 parts by mass of a hydrocarbon surfactant are blended with respect to 100 parts by mass of the resin. The resin comprises a low density polyethylene resin and / or an ethylene-vinyl acetate copolymer resin, and the hydrocarbon surfactant is a partial ester of a polyhydric alcohol and a fatty acid, or an alkylene oxide thereof. It is at least one selected from the group consisting of addition compounds.

  A second invention is characterized in that, in the first invention, the amount of the hydrocarbon-based surfactant is at least 8 times the amount of the fluorine-based surfactant.

  The third invention is a method for producing a master batch pellet containing a resin, a fluorine-based surfactant, and a hydrocarbon-based surfactant. The above production method is a first step in which a resin composed of a low-density polyethylene resin and / or an ethylene-vinyl acetate copolymer resin charged into a first hopper of a twin-screw extruder is melted by the twin-screw extruder. A second step of injecting into the twin-screw extruder the fluorine-based surfactant and the hydrocarbon-based surfactant charged into the second hopper downstream from the first hopper in the twin-screw extruder, and A third step of kneading the resin, the fluorosurfactant and the hydrocarbon surfactant with a twin screw extruder, the resin kneaded in the third step, and the fluorosurfactant And a fourth step of extruding and pelletizing a mixture of the above-mentioned hydrocarbon-based surfactant.

  In a fourth aspect based on the third aspect, the hydrocarbon-based surfactant introduced into the second hopper is a partial ester of a polyhydric alcohol and a fatty acid, or an alkylene oxide addition compound thereof. It is at least one selected from the group consisting of:

  According to a fifth invention, in the third or fourth invention, the second step is characterized in that the heated hydrocarbon surfactant is injected into the twin-screw extruder.

  According to a sixth aspect of the present invention, in the third or fourth aspect of the invention, in the second step, the fluorosurfactant and the hydrocarbon surfactant heated to 50 ° C. to 100 ° C. It is injected into a screw extruder.

  7th invention is a preparation method of the masterbatch pellet containing resin, a fluorochemical surfactant, and a hydrocarbon type surfactant. In the above method, the resin and the fluorine-based interface are adjusted so that the fluorine-based surfactant is 0.45 to 5 parts by mass and the hydrocarbon-based surfactant is 4 to 48 parts by mass with respect to 100 parts by mass of the resin. The activator and the hydrocarbon-based surfactant are melt kneaded and extruded into pellets.

  According to the present invention, it is possible to provide a master batch pellet that can suppress generation of corrosive gas during production and prevent corrosion of a production machine, and a production method thereof.

  As a result of intensive studies, the present applicant has produced master batch pellets in which a polyolefin-based resin is blended with a fluorine-based surfactant and a hydrocarbon-based surfactant. Specifically, in the master batch pellet according to the present invention, the fluorosurfactant is 0.45 with respect to 100 parts by mass of polyolefin resin (low density polyethylene resin and / or ethylene-vinyl acetate copolymer resin). ~ 5 parts by mass and 4 to 48 parts by mass of a hydrocarbon-based surfactant are blended. In addition, the compounding amount of the hydrocarbon-based surfactant in the master batch pellet according to the present invention is preferably at least 8 times or more, more preferably 20 times or more, the compounding amount of the fluorine-based surfactant.

  In addition, although a master batch pellet may be called a master pellet and a master batch, in this description, it is called a master batch pellet.

  Hereinafter, the present invention will be described in detail, but these descriptions do not limit the present invention. Accordingly, it goes without saying that various improvements and modifications can be made without departing from the scope of the present invention.

  Examples of the polyolefin resin in the master batch pellet according to the present invention include a low density polyethylene resin, a linear low density polyethylene resin, and an ethylene-vinyl acetate copolymer resin. In addition, the polyolefin resin in the masterbatch pellet according to the present invention may be used alone or in combination of two or more of the above-mentioned resins. However, in consideration of the moldability of the masterbatch pellet, the polyolefin resin is vinyl acetate. An ethylene-vinyl acetate copolymer resin (hereinafter referred to as EVA resin) having a content of about 5% to 15% is preferred.

  Examples of the fluorosurfactant include an anionic surfactant (perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate, etc.), and a cationic surfactant (perfluoroalkyltrimethylammonium). Salts), nonionic surfactants (such as oligomers containing perfluoroalkyl groups and hydrophilic groups, oligomers containing perfluoroalkyl groups and lipophilic groups, urethanes containing perfluoroalkyl groups and lipophilic groups), An amphoteric surfactant (perfluoroalkyl betaine etc.), a nonionic surfactant, etc. can be mentioned. In the master batch pellet according to the present invention, the above-mentioned various surfactants may be used alone as a fluorine-based surfactant, or two or more kinds may be appropriately combined.

  Moreover, as a fluorine-type surfactant of the masterbatch pellet which concerns on this invention, the well-known fluorine-type surfactant made from AGC Seimi Chemical Co., Ltd. and Daikin Industries, Ltd. can be used, for example. Details of the product name and the like will be described later.

  Next, examples of the hydrocarbon surfactant include a polyhydric alcohol partial ester compound composed of a polyhydric alcohol and a fatty acid, or an alkylene oxide addition compound thereof. More specifically, for example, sorbitan surfactants (such as sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan monobehenate), glycerin surfactant (glycerin monopalmiate) Tate, glycerol monostearate, glycerol monolaurate, glycerol monooleate, diglycerol monopalmitate, diglycerol monostearate, polyglycerol laurate, polyglycerol oleate, polyglycerol stearate, etc.), polyethylene Glycol-based surfactants (polyethylene glycol monostearate, polyethylene glycol monopalmitate, polyethylene glycol alkyl phenyl ether, etc.), trimer Roll propane surfactant (trimethylolpropane monostearate, trimethylolpropane distearate, trimethylolpropane tristearate, etc.), pentaerythritol surfactant (pentaerythritol monopalmitate, pentaerythritol monostearate, etc.) , Etc. In the masterbatch pellet according to the present invention, the above-mentioned various surfactants may be used alone as a hydrocarbon-based surfactant, or two or more kinds may be appropriately combined.

  Moreover, as a hydrocarbon-type surfactant of the masterbatch pellet which concerns on this invention, the well-known hydrocarbon-type surfactant by Riken Vitamin Co., Ltd. can be used, for example. Details of the product name and the like will be described later.

  In addition to the fluorosurfactant and hydrocarbon surfactant, the masterbatch pellet according to the present invention includes a plasticizer, a heat stabilizer, an ultraviolet absorber, an antioxidant, and an antistatic agent as necessary. In addition, additives such as pigments and dyes may be appropriately blended.

  Hereinafter, the present invention will be described in more detail on the basis of examples and comparative examples. However, the present invention is not limited to only the examples of the present invention, and each component contained in a quantitative and qualitative range that does not impair the effects of the present invention. You may change the combination and compounding quantity of these.

  According to the compounding amounts described in Table 1, master batch pellets according to Examples 1 to 9 and Comparative Examples 1 to 6 were produced, and the corrosion of the production machine was evaluated. In addition, Examples 1-9 of Table 1 show Examples 1-9, respectively, and ratios 1-6 show Comparative Examples 1-6, respectively.

(Contained ingredients of master batch pellet)
First, the compounding component of the masterbatch pellet which concerns on each of Examples 1-9 and Comparative Examples 1-6 is demonstrated.

  The olefin-based resin (resin component), the fluorine-based surfactant, and the hydrocarbon-based surfactant, which are blending components of the master batch pellets according to each of Examples 1 to 9 and Comparative Examples 1 to 6, are specifically Is as follows. The resin components, fluorine surfactants, and hydrocarbon surfactants in Table 1 are indicated by trade names, and the numerical values indicate the ratios of the fluorine surfactant and the hydrocarbon surfactant to 100 parts by mass of the resin component. It was.

<Resin component>
NUC-8133: High pressure low density polyethylene resin manufactured by Nippon Unicar Co., Ltd. (density 0.923 g / cm ³ , MFR = 1.5 g / 10 min)
Ultrasen 630: EVA resin manufactured by Tosoh Corporation (vinyl acetate content 15% by weight, MFR = 1.5 g / 10 min, melting point 90 ° C.)
NUC-3250: EVA resin manufactured by Nihon Unicar Co., Ltd. (vinyl acetate content 5% by weight, MFR = 1.5 g / 10 min, melting point 105 ° C.)

<Fluorosurfactant>
DS-403N: Fluorine surfactant manufactured by Daikin Industries, Ltd. DS-403: Fluorine surfactant manufactured by Daikin Industries, Ltd. DS-401: Fluorine surfactant manufactured by Daikin Industries, Ltd.

In addition to the above-mentioned fluorine-based surfactants, the following fluorine-based surfactants can also be used.
S-121: Fluorine-based surfactant (cationic) manufactured by AGC Seimi Chemical Co., Ltd.
S-131: Fluorine-based surfactant (amphoteric) manufactured by AGC Seimi Chemical Co., Ltd.
S-141: Fluorine-based surfactant (nonionic) manufactured by AGC Seimi Chemical Co., Ltd.
S-381: Fluorine-based surfactant (nonionic) manufactured by AGC Seimi Chemical Co., Ltd.
S-382: Fluorine-based surfactant manufactured by AGC Seimi Chemical Co., Ltd.

  In addition, as shown to the formulation examples 1-4 of Table 2, the hydrocarbon type surfactant which is a compounding component of the masterbatch pellet concerning each of Examples 1-9 and Comparative Examples 1-6 is a plurality of types of hydrocarbons. Combined with a surfactant. Specifically, it is as shown in Table 2 and the following. In addition, the hydrocarbon type surfactant of Table 2 is shown by a brand name, and a numerical value is weight%.

<Hydrocarbon-based surfactant>
A-631E: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (Sorbitan palmitate / ethylene oxide 3 mol adduct, melting point 44 ° C., HLB value = 8.1)
A-648E: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (Sorbitan stearate / ethylene oxide 1 mol adduct, melting point 45 ° C., HLB value = 6.9)
AF-004: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (Sorbitan palmitate / propion oxide adduct, melting point 47 ° C., HLB value = 6.1)
AF-75: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (triglyceryl stearate, melting point 56 ° C., HLB value = 5.6)
O-71-D: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (diglycerin oleate, liquid, HLB value = 5.7)
P-300: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (Sorbitan palmitate with a purity of 85% valmitic acid, melting point 55 ° C. to 61 ° C., HLB value = 5.6)
SP-250: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (sorbitan palmitate having a purity of 70% valmitic acid, melting point 50 ° C. to 56 ° C., HLB value = 4.8)

In addition to the above hydrocarbon surfactants, the following carbon surfactants can also be used.
A-7412: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (triglycerin monostearate, melting point 57 ° C., HLB value = 6.3)
A-7414: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (triglycerin distearate, melting point 56 ° C., HLB value = 5.6)
A-7546: Hydrocarbon surfactant (glycerin oleate) manufactured by Riken Vitamin Co., Ltd.
AF-75: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (triglyceryl stearate, melting point 56 ° C., HLB value = 5.6)
HC-100: Hydrocarbon surfactant (glyceryl hydroxystearate) manufactured by Riken Vitamin Co., Ltd.
J-6081: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (polyglycerin stearate, liquid, HLB value = 9)
L-71-D: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (diglycerin laurate, liquid, HLB value = 7.3)
M-300: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (glycerin monolaurate, melting point 54 ° C. to 60 ° C., HLB value = 5.4)
OL-100E: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (glycerin monooleate, melting point 37 ° C. to 43 ° C., HLB value = 4.3)
P-100S: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (High purity palmitic acid monoglyceride, melting point 72 ° C., HLB value = 4.3)
S-100A: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (glycerin monostearate, melting point 63 ° C. to 68 ° C., HLB value = 4.3)
S-200: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (glycerin mono-distearate, melting point 56 ° C. to 62 ° C., HLB value = 3.2)
S-300W: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (sorbitan stearate (sorbitol ester type), melting point 59 ° C. to 63 ° C., HLB value = 5.4)
S-60: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (Sorbitan stearate (sorbitan ester type), melting point 50 ° C. to 56 ° C., HLB value = 5)
S-71-D: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (diglyceryl stearate, melting point 55 ° C. to 61 ° C., HLB value = 5.7)
S-72: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (diglycerin distearate, melting point 53 ° C. to 59 ° C., HLB value = 4.4)
SA-3355: Hydrocarbon surfactant (glycerin stearate) manufactured by Riken Vitamin Co., Ltd.
S-95: Hydrocarbon surfactant manufactured by Riken Vitamin Co., Ltd. (glycerin stearate, melting point 55 ° C. to 57 ° C., HLB value = 1.9)

(Manufacturing method of master batch pellet)
Next, the manufacturing method of the masterbatch pellet which concerns on each of Examples 1-9 and Comparative Examples 1-6 is demonstrated.

The resin component shown in Table 1 was charged from the hopper of the production machine, and after the above-described resin components were in a molten state, the above-described fluorine system was heated to about 60 to 70 ° C. from the intermediate portion of the production machine. Surfactant and hydrocarbon surfactant were added. And it knead | mixed and kneaded with the said preparation machine, and it hot-cut at the front-end | tip of the said preparation machine, and produced the masterbatch pellet concerning each of Examples 1-9 and Comparative Examples 1-6.
Production machine: Twin screw extruder manufactured by Nippon Steel Works, Ltd., trade name TEX65αII

(Evaluation)
According to Table 1, after producing master batch pellets according to Examples 1 to 9 and Comparative Examples 1 to 6 using the production machine, changes in the colors of the cylinder and screw of the production machine after 14 days were evaluated. . Specifically, the following criteria were used for visual evaluation.
○: No color change △: Partial color change ×: Overall color change

  As shown in the "Evaluation" column of Table 1, none of the master batch pellets according to Examples 1 to 9 showed any change in the color of the cylinder and screw of the production machine, and the cylinder and screw were corroded. It was confirmed that there was no.

  On the other hand, as shown in the “Evaluation” column of Table 1, changes in the colors of the cylinders and screws of the production machines were confirmed for all of the master batch pellets according to Comparative Examples 1 to 4. In particular, for the master batch pellet according to Comparative Example 1, a change in the color of the entire cylinder and screw of the production machine was confirmed. This is presumably because the fluorine-based surfactant blended in the master batch pellet was decomposed when melt-kneaded by the production machine, and hydrogen fluoride, dioxane and the like were generated.

  Moreover, although the master batch pellet which concerns on the comparative example 5 did not change the color of the cylinder and screw of a production machine, there is a problem in productivity (cost). That is, for example, when an agricultural film is produced using masterbatch pellets and the agricultural film becomes the outer wall of the house, the crops grown in the house are prevented from getting wet, It is required to have the capability of preventing water vapor from condensing on the inside of the agricultural film) and preventing water droplets from dropping on the crops in the house. Therefore, a certain amount of fluorine-based surfactant needs to be blended in the agricultural film. Therefore, since the master batch pellet according to Comparative Example 5 contains a relatively small amount of the fluorine-containing surfactant, the agricultural film is used to keep a certain amount of the fluorine-containing surfactant in the agricultural film. This is because many master batch pellets are required for production.

  In addition, since the masterbatch pellet which concerns on the comparative example 6 had many compounding quantities of hydrocarbon type surfactant, it was not able to be extruded using the said preparation machine.

  Thus, the master batch pellet according to each of Examples 1 to 9 can suppress the generation of corrosive gas during production and prevent corrosion of the production machine or the like. Moreover, since the fluorine-based surfactant and the hydrocarbon-based surfactant are blended in the masterbatch pellets according to each of Examples 1 to 9, if the masterbatch pellet is used for production of an agricultural film, for example, Compared to the case where an agricultural film is produced using a master batch pellet containing only one of a fluorosurfactant and a hydrocarbon surfactant, the performance required for the agricultural film as described above is further obtained. be able to. Moreover, since the fluorine-type surfactant and the hydrocarbon-type surfactant are mix | blended with the masterbatch pellet which concerns on each of Examples 1-9, when producing an agricultural film, a fluorine-type surfactant and This eliminates the trouble of separately blending the hydrocarbon-based surfactant and improves the productivity.

  In addition, you may produce an agricultural film using the masterbatch pellet which concerns on each of Examples 1-9. Hereinafter, the agricultural film using the masterbatch pellet which concerns on each of Examples 1-9 is demonstrated.

  The agricultural film using the masterbatch pellets according to each of Examples 1 to 9 is obtained by applying the masterbatch pellets according to each of Examples 1 to 9 to a resin (hereinafter simply referred to as a base resin) serving as the base of the agricultural film. It is produced by forming a film by combining one or more kinds.

  The base resin is preferably transparent and flexible, and examples thereof include olefin resins such as EVA resin, polyethylene resin, and polypropylene resin.

  Moreover, the base resin in the agricultural film according to the present invention may be used alone or in combination of two or more thereof, and if necessary, the base resin may be added with a plasticizer, a heat stabilizer, an ultraviolet absorber, an antioxidant. You may mix | blend additives, such as an agent, an antistatic agent, a pigment, and dye, suitably. In consideration of moldability and the like, the base resin is preferably an ethylene-vinyl acetate copolymer resin having a vinyl acetate content of about 10% to 15%.

  The masterbatch pellet according to the present invention and the method for producing the masterbatch pellet are suitable, for example, as a masterbatch pellet for producing a film or the like that serves as an outer wall of a house made of a metal pipe or the like as a framework.

Claims (7)

A master batch pellet containing a resin, a fluorosurfactant and a hydrocarbon surfactant,
The master batch pellet is blended with 0.4 to 5 parts by mass of a fluorosurfactant and 4 to 48 parts by mass of a hydrocarbon surfactant with respect to 100 parts by mass of the resin.
The resin comprises a low density polyethylene resin and / or an ethylene-vinyl acetate copolymer resin,
Master batch pellets, wherein the hydrocarbon surfactant is at least one selected from the group consisting of partial esters of polyhydric alcohols and fatty acids, or alkylene oxide addition compounds thereof.   2. The master batch pellet according to claim 1, wherein the blending amount of the hydrocarbon-based surfactant is at least 8 times the blending amount of the fluoro-surfactant. A method for producing a masterbatch pellet containing a resin, a fluorosurfactant and a hydrocarbon surfactant,
A first step of bringing a resin composed of a low density polyethylene resin and / or an ethylene-vinyl acetate copolymer resin charged into a first hopper of a twin screw extruder into a molten state with the twin screw extruder;
A second step of injecting into the twin-screw extruder a fluorine-based surfactant and a hydrocarbon-based surfactant charged into a second hopper downstream from the first hopper in the twin-screw extruder;
A third step of kneading the resin, the fluorosurfactant and the hydrocarbon surfactant with the twin-screw extruder;
A master batch pellet manufacturing method comprising: a fourth step of extruding and pelletizing a mixture of the resin, the fluorosurfactant and the hydrocarbon surfactant kneaded in the third step.   The hydrocarbon surfactant charged into the second hopper is at least one selected from the group consisting of partial esters of polyhydric alcohols and fatty acids, or alkylene oxide addition compounds thereof. The manufacturing method of the masterbatch pellet of Claim 3.   5. The method for producing master batch pellets according to claim 3, wherein in the second step, the heated hydrocarbon-based surfactant is injected into the twin-screw extruder.   The second step is characterized in that the fluorine-based surfactant and the hydrocarbon-based surfactant heated to 50 ° C to 100 ° C are injected into the twin-screw extruder. Alternatively, a method for producing a master batch pellet according to 4. A method for producing a masterbatch pellet containing a resin, a fluorosurfactant and a hydrocarbon surfactant,
With respect to 100 parts by mass of the resin, the resin, the fluorosurfactant, and the resin so that the fluorosurfactant is 0.45 to 5 parts by mass and the hydrocarbon surfactant is 4 to 48 parts by mass. A master batch pellet manufacturing method in which a hydrocarbon surfactant is melt-kneaded and extruded into pellets.