JP2010159403A - Resin composition for filament, and the resultant filament - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition capable of obtaining filaments excellent in the bleeding performance of an insect-controlling agent in the initial stage of use thereof. <P>SOLUTION: The resin composition for filaments includes 100 pts.wt. of a high-density polyethylene; 0.1-10 pts.wt. of a pest-controlling agent based on 100 pts.wt. of the high-density polyethylene; and 0.1-10 pts.wt. of synthetic silica based on 100 pts.wt. of the high-density polyethylene. In the resin composition, the density of the high-density polyethylene is 935-965 kg/m<SP>3</SP>, the MFR of the high-density polyethylene is 0.1-6 g/10 min, and the average micropore radius of the synthetic silica is 0.040-0.105 μm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition for filaments and a filament comprising the resin composition.

  A resin composition obtained by blending a pest control agent with a polyolefin resin such as polypropylene or polyethylene is processed into various molded articles and used as a material for preventing pests such as mites, lice, mosquitoes and flies. For example, Patent Document 1 discloses a composition of a polypropylene resin and a pest control agent, and a filament formed by melt spinning the composition. Moreover, in patent document 2, the collar which consists of a composition of linear low density polyethylene and a pest control agent, and this composition is known. Patent Document 3 discloses a filament resin composition containing an ethylene-α-olefin copolymer and an insect repellent. Patent Document 4 discloses a filament resin composition containing an ethylene homopolymer and an insect repellent. Further, Patent Document 5 discloses a polymer composition containing an olefin polymer, an insect repellent, and an insect repellent holder, and a fiber made of the polymer composition.

Japanese Patent Laid-Open No. 4-65509 JP-A-6-315332 JP 2008-031431 A JP 2008-031619 A JP 2008-106232 A

However, when a conventional resin composition containing a polyolefin resin and a pest control agent is formed into a filament, further improvement in the bleeding property of the pest control agent at the initial use is required.
Under such circumstances, the problem to be solved by the present invention is to provide a resin composition from which a filament excellent in bleedability of a pest control agent in the initial stage of use can be obtained, and a filament comprising the resin composition.

  According to the present invention, a resin composition for filaments containing high-density polyethylene, a pest control agent and synthetic silica, and a resin composition capable of obtaining a filament excellent in bleeding property of an early use pest control agent, and a resin composition Can be provided.

That is, the first of the present invention is a resin composition containing high density polyethylene, a pest control agent and synthetic silica, wherein the density of the high density polyethylene is 935 to 965 kg / m ³ and the MFR is 0.1 to 6 g / 10 min. The average pore radius of the synthetic silica is 0.040 to 0.105 μm, and 100 parts by weight of high-density polyethylene and 100 to 10 parts by weight of the high-density polyethylene contain 0.1 to 10 pest control agents. It relates to a resin composition for filaments containing 0.1 part by weight and 0.1 to 10 parts by weight of synthetic silica.

The second of the present invention relates to a filament comprising the above resin composition for filaments.

  The resin composition for filaments of the present invention is a resin composition containing high-density polyethylene, a pest control agent and synthetic silica, and 100 parts by weight of the high-density polyethylene and the pest control agent with respect to 100 parts by weight of the high-density polyethylene. Is a resin composition for filaments containing 0.1 to 10 parts by weight and 0.1 to 10 parts by weight of synthetic silica.

The content of the pest control agent is 0.1 to 10 parts by weight per 100 parts by weight of high density polyethylene.
The content of the pest control agent is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, from the viewpoint of preventing stickiness of the composition before being formed into a filament. Moreover, from a viewpoint of improving insect-proof performance, Preferably it is 0.5 weight part or more, More preferably, it is 1 weight part or more.

The content of synthetic silica in the resin composition of the present invention is 0.1 to 10 parts by weight per 100 parts by weight of high density polyethylene.
The content of the synthetic silica is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, from the viewpoint of preventing filament breakage. Moreover, from a viewpoint of suppressing the stickiness of the composition before shape | molding a filament, Preferably it is 0.5 weight part or more, More preferably, it is 1 weight part or more.

  The high-density polyethylene used in the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin. From the viewpoint of increasing the strength of the filament, a copolymer of ethylene and α-olefin is preferable. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene, and the like. May be used alone or in combination of two or more. In addition, this density is measured in accordance with the method prescribed | regulated to A method among JISK7112-1980 using the test piece which annealed according to the method of the low density polyethylene as described in JISK6760-1995.

  The content of the monomer unit based on ethylene in the high-density polyethylene is usually 90 to 100% by weight with respect to the total weight (100% by weight) of the high-density polyethylene. The content of the monomer unit based on the α-olefin is usually 0.1 to 10% by weight with respect to the total weight (100% by weight) of the high-density polyethylene.

  Examples of high density polyethylene include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and ethylene-1-butene-1-hexene copolymer. Examples thereof include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, and an ethylene-1-hexene copolymer.

  The melt flow rate (MFR) of the high density polyethylene is 0.1 to 6 g / 10 min. The MFR is preferably 0.3 g / 10 min or more, more preferably 0.6 g / 10 min or more from the viewpoint of improving melt extrudability. Further, the MFR is preferably 4 g / 10 min or less, more preferably 2 g / 10 min or less, from the viewpoint of improving heat stretchability and mechanical strength. The MFR is measured under the conditions of a load of 21.18 N and a temperature of 190 ° C. in the method defined in JIS K7210-1995.

  The melt flow rate ratio (MFRR) of the high-density polyethylene is preferably 50 or less, more preferably 45 or less, and still more preferably 40 or less, from the viewpoint of improving melt spinnability. The MFRR is preferably 10 or more, more preferably 15 or more, and still more preferably 20 or more, from the viewpoint of improving melt extrudability. The MFRR is obtained by measuring the melt flow rate (MFR-H, unit: g / 10 minutes) measured under the conditions of a test load of 211.83 N and a measurement temperature of 190 ° C. according to JIS K7210-1995, in accordance with JIS K7210. -In the method specified in 1995, this is a value divided by the melt flow rate (MFR) measured under the conditions of a load of 21.18 N and a temperature of 190 ° C.

The density of the high density polyethylene is 935 to 965 kg / m ³ . From the viewpoint of improving heat stretchability, it is preferably 960 kg / m ³ or less, more preferably 955 kg / m ³ or less, and further preferably 950 kg / m ³ or less. Moreover, it said seal degree, from the viewpoint of enhancing the heat stretchability, preferably 940 kg / m ³ or more, more preferably 945 kg / m ³ or more. The density is measured according to the method defined in Method A of JIS K7112-1980 using a test piece annealed according to the method of low density polyethylene described in JIS K6760-1995.

  As a method for producing high-density polyethylene, known olefin polymerization catalysts such as Ziegler-Natta catalysts, chromium catalysts, metallocene catalysts, solution polymerization methods, slurry polymerization methods, gas phase polymerization methods, high pressure ion polymerization methods are used. And the like, and a production method by a known polymerization method. The polymerization method may be either a batch polymerization method or a continuous polymerization method, and may be a multistage polymerization method having two or more stages.

Examples of the Ziegler-Natta catalyst include the following catalyst (1) or (2).
(1) A catalyst comprising a component in which at least one selected from the group consisting of titanium trichloride, vanadium trichloride, titanium tetrachloride and titanium haloalcolate is supported on a magnesium compound carrier, and an organometallic compound as a cocatalyst ( 2) A catalyst composed of a coprecipitate of a magnesium compound and a titanium compound or an eutectic and an organometallic compound as a cocatalyst.

  Examples of the chromium-based catalyst include a catalyst composed of synthetic silica or a component having a chromium compound supported on synthetic silica lumina and an organometallic compound as a cocatalyst.

Examples of the metallocene catalyst include the following catalysts (1) to (4).
(1) A catalyst comprising a transition metal compound having a group having a cyclopentadiene skeleton and a component containing an alumoxane compound. (2) A component containing the transition metal compound, and ionic properties such as trityl borate and anilinium borate. catalyst comprising component containing a compound (3) said transition metal compound and component comprising a component containing an ionic compound, a catalyst (4) SiO ₂ the components of the consisting of components including an organic aluminum compound, Al ₂ Catalyst obtained by supporting or impregnating an inorganic particulate carrier such as O ₃ or a particulate polymer carrier such as an olefin polymer such as ethylene or styrene.

  As a method for producing high-density polyethylene, a production method using a Ziegler-Natta catalyst or a metallocene catalyst is preferred. In addition, from the viewpoint of improving melt spinnability, those having a short residence time distribution during polymerization are preferable. In order to shorten the residence time distribution, a plurality of reaction vessels are arranged in parallel in a single-stage polymerization or a process having a plurality of reaction vessels. It is preferable that the polymer is run and polymerized.

  Examples of the pest control agent in the present invention include compounds having an insecticidal activity, such as insecticides, insect growth regulators, and repellents.

  Examples of the insecticide include pyrethroid compounds, organophosphorus compounds, carbamate compounds, and phenylpyrazole compounds. Examples of pyrethroid compounds include permethrin, allethrin, d-alleslin, dd-arethrin, d-tetramethrin, prareslin, d-phenothrin, d-resmethrin, empentrin, fenvalerate, esfenvalerate, fenpropathrin, cyhalothrin, etofenprox , Traromesrin, esbioslin, benfluthrin, teraleslin, deltamethrin, phenothrin, tefluthrin, bifenthrin, cyfluthrin, cypermethrin, alpha cypermethrin, and the like. , Calclofos, salicione, diazinon, etc., and carbamate compounds include methoxy Azone, propoxur, Fenobukabu, carbaryl and the like, fipronil and the like as the phenylpyrazole compound.

  Insect growth regulators include pyriproxyfen, mesoprene, hydroprene, diflubenzuron, cyromazine, phenoxy curve, lufenuron (CGA184599) and the like.

  Examples of repellents include diethyl toluamide and dibutyl phthalate.

  These pest control agents can be used alone or in admixture of two or more. Moreover, you may use together the compound which has a role which raises the effect of insect-proof activity. Examples of the compound include piperonyl butoxide, MGK264, octachlorodipropyl ether and the like.

As the pest control agent, insecticides are preferable, pyrethroid compounds are more preferable, and pyrethroid compounds having a vapor pressure at 25 ° C. of less than 1 × 10 ⁻⁶ mmHg are more preferable. Examples of pyrethroid compounds having a vapor pressure of less than 1 × 10 ⁻⁶ mmHg at 25 ° C. include pyriproxyfen, resmesrin, permethrin and the like.

The synthetic silica used in the present invention is a silica synthesized by a precipitation method or a gel method, and examples thereof include powdered silicic acid and white carbon.
As the synthetic silica, amorphous synthetic silica is preferable.

  The average pore radius of the synthetic silica used in the present invention is 0.040 to 0.105 μm. From the viewpoint of enhancing the bleeding property of the pest control agent at the initial stage of use, the upper limit of the average pore radius is preferably 0.090 μm or less, more preferably 0.080 μm or less, and further preferably 0.070 μm or less. The lower limit of the average pore radius is preferably 0.050 μm or more, and more preferably 0.060 μm or more. The average pore radius is measured by a mercury intrusion method.

The specific surface area of the synthetic silica used in the present invention is preferably 240 m ² / g or less, more preferably 210 m ² / g or less, from the viewpoint of enhancing the bleeding property of the pest control agent at the initial stage of use. Moreover, from a viewpoint of improving the bleeding property of the pest control agent at the initial stage of use, it is preferably 50 m ² / g or more, more preferably 80 m ² / g or more, and further preferably 110 m ² / g or more. The specific surface area is measured by a nitrogen adsorption BET method.

  The oil absorption weight W (g / 100 g), which is the weight of the pest control agent held per 100 g of synthetic silica, is preferably 1000 g / 100 g or less from the viewpoint of improving the bleeding property of the pest control agent in the initial stage of use. Preferably it is 500 g / 100 g or less, More preferably, it is 350 g / 100 g or less. From the viewpoint of enhancing the retention of the pest control agent, it is preferably 30 g / 100 g or more, more preferably 60 g / 100 g or more, and more preferably 120 g / 100 g or more.

  The content of the pest control agent in the resin composition of the present invention is preferably (5 × W) with respect to 100 parts by weight of the synthetic silica when the oil absorption weight of the synthetic silica pest control agent is W (g / 100 g). It is not more than parts by weight, more preferably not more than (3 × W) parts by weight, and still more preferably not more than (W) parts by weight.

  In the resin composition of the present invention, additives such as an antioxidant, an anti-blocking agent, a filler, a lubricant, an antistatic agent, a weathering stabilizer, a pigment, a processability improver, a metal soap, etc .; Polymer components other than polyethylene may be blended, and two or more of these additives and polymer components may be used in combination.

  The resin composition of the present invention can be obtained by melt-kneading a high-density polyethylene, a pest control agent and synthetic silica and, if necessary, other components by a known method. For example, a method in which high-density polyethylene, a pest control agent, and synthetic silica are mixed in advance, and the resulting mixture is melt-kneaded using an extruder, a roll molding machine, a kneader, or the like, a high-density polyethylene, a pest control agent, and synthetic silica Separately supplying to an extruder, roll molding machine, kneader, etc., melt mixing, supplying premixed synthetic silica and pest control agent and high density polyethylene to an extruder, roll molding machine, kneader, etc. Examples thereof include a melt mixing method, a method in which high-density polyethylene and synthetic silica are mixed in advance, and a pest control agent separately supplied to an extruder, a roll molding machine, a kneader and the like and melt kneaded. Moreover, when melt-kneading with an extruder, you may inject | pour from the middle of an extruder using addition apparatuses, such as a side extruder or a feeder.

  In the production of the resin composition, preferably, the pest control agent is used as a pest control agent-supported body treated, supported, supported, impregnated, infiltrated, injected, adsorbed, absorbed, etc., on synthetic silica.

  The pest control agent or silica, or the pest control agent and silica, or the above-mentioned pest control agent holding body is used as a master batch added to the resin, and melt-kneaded with high-density polyethylene to produce the resin composition of the present invention. Also good. Preferably, it is a method of using it as a master batch in which a pest control agent holding body is added to a resin.

  Examples of the resin used as the base of the masterbatch include olefin resins such as ethylene resins, propylene resins, butene resins, 4-methyl-1-pentene resins, modified products thereof, saponified products, and hydrogenated products. Can do. Preferably, high-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, linear ultra-low-density polyethylene, high-pressure process low-density polyethylene, ethylene-based resins such as ethylene-vinyl acetate copolymer; butadiene Examples thereof include hydrogenated polymers.

  In the production of the resin composition, when a master batch is used, the compounding amount of the master batch is usually less than 50 parts by weight with respect to 100 parts by weight of the high-density polyethylene contained in the resin composition of the present invention, and the viewpoint of improving economy Therefore, 20 parts by weight or less is preferable, and 10 parts by weight or less is more preferable.

  Since the resin composition of the present invention is excellent in melt spinnability and good melt extrudability, it is molded into a filament such as a multifilament or a monofilament. Preferably, it is formed into a monofilament and used. Moreover, the filament which consists of this resin composition is excellent in heat drawability, and its mechanical strength is also favorable. Furthermore, the method for producing a filament using the resin composition is excellent in cost because the resin composition can be extruded and spun at a high discharge rate to perform high-stretching by a single-stage stretching operation.

  As a method for forming the resin composition of the present invention into a filament, a known molding method such as a melt spinning method or a (direct) spinning / stretching method is used. For example, the resin composition is melted using an extruder or the like, and a gear pump is used. After passing through, for example, melt extrusion from a die / nozzle to form a strand, take out the melt-extruded strand resin composition, cool it with a cooling medium such as water or air, perform spinning, and then If necessary, a method such as heat stretching, heat treatment, oil coating, and the like can be performed and wound up.

  Examples of the cross-sectional shape of the filament include a circle, an ellipse, a triangle, a quadrangle, a hexagon, and a star.

  The filament is usually in the range of 50 to 500 denier, preferably 100 to 350 denier, more preferably 150 to 250 denier.

  The filaments made of the resin composition of the present invention can be used as monofilaments, nets and nets such as mosquito nets, screen doors, insect nets, ropes, yarns, filters, etc., and as multifilaments, ropes, nets, carpets Non-woven fabric; filter; shoes; clothing and the like. In particular, applications requiring insect repellent properties such as screen doors, insect screens, mosquito nets, filters, carpets, shoes, and clothing are suitable.

  Examples of the insects to be protected against the insects of the filaments made of the resin composition of the present invention include arthropods such as spiders, ticks and insects. Further examples will be described as follows. Examples of the scabbard include acarid mites (Acarina), citrus mite, mite mite, etc .; Examples of labrums include gejis belonging to the order of Scutigeromorpha; yssun centipedes belonging to the order of Lithobiomorpha. In the double leg class, for example, the zelkova and red scallops belonging to the Polydesmoidea are listed.

  Examples of insects include the following. Yamatoshimi, etc. belonging to Thysanura; Camellia, Kera, Enma cricket, Tosamabata, Sabakubi-batta, locust, etc. belonging to Orthoptera; Scissors, etc. belonging to Dermaptera; Blattaria , Black cockroaches, cockroaches, cockroaches, etc.; Yamato termites, termites, termites, etc.; Ants that belong to the order of Psocoptera, etc.; Cat lice, etc .; body lice belonging to the order of Anoplura, white lice, human lice, etc .; Mi, Kusagi-kamemushi, etc .; Coleoptera (Coleoptera) cutworm, cucumber weevil, weevil, slatted beetle, Nagaryo hornworm, Japanese beetle, etc .; Akaieka, Aedes aegypti, Anopheles, Buyu, Sesuji Rika, Butterfly flies, House flies, Flies flies, Tsetse flies, Cows, Flies, etc .; Hornets (Hymenoptera)

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties in Examples and Comparative Examples were measured according to the following methods.

(1) Melt flow rate (MFR, unit: g / 10 minutes)
In the method defined in JIS K7210-1995, the measurement was performed under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(2) Melt flow rate ratio (MFRR)
In the method specified in JIS K7210-1995, the melt flow rate (MFR-H, unit: g / 10 minutes) measured under conditions of a test load of 211.83 N and a measurement temperature of 190 ° C. is specified in JIS K7210-1995. In this method, the value divided by the melt flow rate (MFR) measured under the conditions of a load of 21.18 N and a temperature of 190 ° C. was defined as MFRR.

(3) Density (Unit: kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. In addition, the measurement sample piece was annealed according to the method of low density polyethylene described in JIS K6760-1995 and used for measurement.

(4) Average pore radius (unit: μm)
After the synthetic silica was dried at 120 ° C. for 4 hours, the pore distribution was measured with a pore radius of about 0.0018 to 100 μm using Autopore III9420 manufactured by MICROMERITICS, and the mercury intrusion ratio was all mercury. The pore radius that was 50% of the amount of penetration was taken as the average pore radius.

(5) Specific surface area (unit: m ² / g)
The synthetic silica to be measured was previously degassed at 120 ° C. for 8 hours. Using a BELSORP-mini made by Nippon BEL Co., Ltd., the adsorption desorption isotherm was measured with nitrogen as the adsorbate under the conditions of an adsorption volume of 77K and an adsorbate cross-sectional area of 0.162 nm ² by the constant volume method. Was calculated by the BET multipoint method.

(6) Oil absorption weight (unit: g / 100g)
Weigh out 5 cm ³ as a pest control agent, add to a glass container, add a little while adding synthetic silica heated to 50 ° C while stirring, and eliminate the ball-shaped product where the drug is localized on the synthetic silica. Synthetic silica was added until. It was determined that the pest control agent was retained when the ball-shaped product disappeared, and the oil absorption weight of the pest control agent per 100 g of synthetic silica was calculated from the added weight of the added synthetic silica and the weight of the pest control agent.

Example 1
1. Preparation of Pest Control Retainer Permethrin (trade name: Exmine; density: 1.21 g / cm ³ ) 51 parts by weight as a pest control agent and 1.5 parts by weight of butylhydroxytoluene as an antioxidant were added. Next, 47.5 parts by weight of Solex CM (manufactured by Tokuyama Corporation; hereinafter referred to as “Silica 1”; physical properties are shown in Table 1) as a synthetic silica is added and mixed with stirring to contain a pest control agent. An insect repellent holder (hereinafter referred to as insect repellent-containing holder A) was obtained.
Next, 60.3 parts by weight of high-pressure low-density polyethylene (trade name: Sumikasen G803-1; MFR = 20 g / 10 min, density = 918 kg / m ³ ) manufactured by Sumitomo Chemical Co., Ltd., and 34.2 parts by weight of the insect repellent-containing holder A And 5.5 parts by weight of zinc stearate were kneaded for 5 minutes under the conditions of a preset temperature of 150 ° C. and a rotation speed of 300 rpm using a Banbury mixer to obtain a pest control agent holding body master batch.

2. Preparation of resin composition for filament 100 parts by weight of high-density polyethylene (trade name: HIZEX 440M manufactured by Prime Polymer; MFR = 0.9 g / 10 min, density = 948 kg / m ³ , MFRR = 35, ethylene-propylene copolymer) Then, 14.5 parts by weight of a pest control agent holding body master batch was kneaded using a Banbury mixer to prepare a resin composition for filaments. There was no stickiness of the resin composition.

3. Manufacture of filament The resin composition for filaments was extruded at a discharge rate of 0.9 kg / hr and a die set temperature of 200 ° C. using a 20 mmφ extruder with a 1.0 mmφ-6 hole die, and taken up at a line speed of 14 m / min. It was drawn at a rate of 112 m / min through a heated water bath and formed into a 200 denier monofilament.

4). Bleed property evaluation 500 mg of the filament was weighed, put in a glass bottle, covered, and allowed to stand in an oven at 60 ° C. for 2 hours. After adding 450 cm ³ of acetone and shaking for 30 minutes, the filament surface was washed. The filament after surface cleaning was put in a glass bottle, covered, placed in an oven at 60 ° C., and allowed to stand for 1 day. The filament was taken out from the oven, 50 cm ³ of ethanol was added, and the mixture was shaken with a shaker for 10 minutes to wash the pest control agent bleed on the surface. The resulting washing solution was measured for permethrin concentration using an ultraviolet-visible spectrophotometer. After wiping off the surface of the filament, it was put in a glass bottle, covered, and allowed to stand again in an oven at 60 ° C. for 6 days. The filament was taken out of the oven again, 50 cm ³ of ethanol was added, and the shaker was shaken for 10 minutes to wash the pest control agent that bleeds on the surface. The resulting cleaning solution was measured for pest control agent concentration using an ultraviolet-visible spectroscopy system.
Measurement of Permethrin Concentration Using an Ultraviolet-Visible Spectrophotometer The surface washing solution was measured under the following conditions using an ultraviolet-visible spectrophotometer V-650 manufactured by JASCO Corporation, and the absorbance of the peak of permethrin in the 200 ± 1 nm range was measured.

UV-Vis spectrophotometer Measurement conditions Cell length 10mm
Bandwidth 2.0nm
Scanning speed 400nm / min
Starting wavelength 340nm
End wavelength 190nm
Data capture interval 1.0nm

Measurements were made in advance with respect to eight ethanol solutions of permethrin having a concentration of 0.632 to 15.8 mg / L using the aforementioned UV-visible spectrophotometer, and the absorbance of the permethrin peak and the concentration of permethrin in the 200 ± 1 nm range were measured. A calibration curve was prepared.
From this calibration curve, the amount of permethrin in the surface cleaning solution was determined.
The amount of permethrin in the washing solution after 1 day divided by the weight of the measured filament is the amount of surface bleed after 1 day, and the amount of permethrin in the washing solution after 6 days after 1 day, that is, after 7 days in total, is the weight of the measured filament. The amount of the surface bleed after 7 days was determined as the amount after removal. The sum of the surface bleed amount after 1 day and the surface bleed amount after 7 days was defined as the cumulative surface bleed amount after 7 days, and the bleed amount at the initial stage of use was evaluated.
The cumulative bleed amount after 7 days of this filament was 2.23 mg / g.

Example 2
The same procedure as in Example 1 was performed except that fine seal CM-F (manufactured by Tokuyama Corporation; hereinafter referred to as silica 2; physical properties are shown in Table 1) was used as the synthetic silica. There was no stickiness of the resin composition.
The cumulative bleed amount after 7 days of this filament was 2.23 mg / g.

Example 3
The same procedure as in Example 1 was performed except that fine seal B (manufactured by Tokuyama Corporation; hereinafter referred to as silica 3; physical properties are shown in Table 1) was used as the synthetic silica. There was no stickiness of the resin composition.
The cumulative bleed amount after 7 days of this filament was 2.70 mg / g.

Example 4
The same procedure as in Example 1 was performed except that fine seal T-32 (manufactured by Tokuyama Corporation; hereinafter referred to as silica 4; physical properties are shown in Table 1) was used as the synthetic silica. There was no stickiness of the resin composition.
The cumulative bleed amount after 7 days of this filament was 2.53 mg / g.

Example 5
The same procedure as in Example 1 was performed except that Carplex FPS-5 (manufactured by Evonik Degussa Japan Co., Ltd .; hereinafter referred to as silica 5; physical properties are shown in Table 1) was used as the synthetic silica. There was no stickiness of the resin composition.
The cumulative bleed amount after 7 days of this filament was 1.73 mg / g.

Example 6
The same procedure as in Example 1 was performed except that Tocsil GU (manufactured by Tokuyama Corporation; hereinafter referred to as silica 6; physical properties are shown in Table 1) was used as the synthetic silica. There was no stickiness of the resin composition.
The cumulative bleed amount after 7 days of this filament was 1.23 mg / g.

Comparative Example 1
The same procedure as in Example 1 was performed except that fine seal X-32 (manufactured by Tokuyama Corporation; hereinafter referred to as silica 7; physical properties are shown in Table 1) was used as the synthetic silica. There was no stickiness of the resin composition.
The cumulative bleed amount after 7 days of this filament was 0.81 mg / g.

Comparative Example 2
The same procedure as in Example 1 was conducted except that Mizukasil P-707 (manufactured by Mizusawa Chemical Industry Co., Ltd .; hereinafter referred to as silica 8; physical properties are shown in Table 1) was used as the synthetic silica. There was no stickiness of the resin composition.
The cumulative bleed amount after 7 days of this filament was 0.54 mg / g.

Comparative Example 3
The same procedure as in Example 1 was performed except that Carplex BS-308N (manufactured by Evonik Degussa Japan Co., Ltd .; hereinafter referred to as silica 9; physical properties are shown in Table 1) was used as the synthetic silica. There was no stickiness of the resin composition.
The cumulative bleed amount after 7 days of this filament was 0.89 mg / g.

Comparative Example 4
The same procedure as in Example 1 was performed except that Sipernat 880 (manufactured by Evonik Degussa Japan Co., Ltd .; hereinafter referred to as silica 10; physical properties are shown in Table 1) was used as the synthetic silica. There was no stickiness of the resin composition.
The cumulative bleed amount after 7 days of this filament was 0.70 mg / g.

Comparative Example 5
The same procedure as in Example 1 was performed except that Nipsil E-743 (manufactured by Tosoh Silica Corporation; hereinafter referred to as silica 11; physical properties are shown in Table 1) was used as the synthetic silica. There was no stickiness of the resin composition.
The cumulative bleed amount after 7 days of this filament was 0.40 mg / g.

Example 7
1. Preparation of a pest control agent holding body To 4.9 parts by weight of permethrin as a pest control agent, 1.9 parts by weight of butylhydroxytoluene as an antioxidant was stirred and dissolved, and then Carplex 80 (Evonik as synthetic silica). Made by Degussa Japan Co., Ltd .; hereinafter referred to as silica 12; physical properties are shown in Table 1) 33.2 parts by weight are added and mixed by stirring, and an insect repellent holder containing a pest control agent (hereinafter referred to as an insect repellent containing holder). B)) was obtained.
Next, 64.9 parts by weight of the high-pressure method low-density polyethylene Sumikasen G803-1; 29.0 parts by weight of the insect repellent-containing support B; and 5.9 parts by weight of zinc stearate are set using a Banbury mixer. The mixture was kneaded for 5 minutes under the conditions of a temperature of 150 ° C. and a rotation speed of 300 rpm to obtain a pest control agent holding body master batch.

2. Preparation of Resin Composition for Filaments 100 parts by weight of high density polyethylene Hi-Zex 440M and 11.8 parts by weight of a pest control agent holding body master batch were kneaded using a Banbury mixer to prepare a resin composition for filaments. There was no stickiness of the resin composition.

3. Filament Production / Bleedability Evaluation As described in Example 1, filament production / bleedability evaluation was performed. The cumulative bleed amount after 7 days of this filament was 2.06 mg / g.

Example 8
1. Preparation of Pest Control Retainer Body 4.9 parts by weight of permethrin as a pest control agent and 1.9 parts by weight of butylhydroxytoluene as an antioxidant are stirred and dissolved, and then Carplex 80D (Evonik) as synthetic silica. Made by Degussa Japan Co., Ltd .; hereinafter referred to as silica 13; physical properties are shown in Table 1) 33.2 parts by weight are added and mixed by stirring, and then an insect repellent holder containing a pest control agent (hereinafter referred to as an insect repellent containing holder). C.).
Next, 64.9 parts by weight of the high-pressure method low-density polyethylene Sumikasen G803-1; 29.0 parts by weight of the insect repellent-containing support C; and 5.9 parts by weight of zinc stearate are set using a Banbury mixer. The mixture was kneaded for 5 minutes under the conditions of a temperature of 150 ° C. and a rotation speed of 300 rpm to obtain a pest control agent holding body master batch.

2. Preparation of Resin Composition for Filaments 100 parts by weight of high density polyethylene Hi-Zex 440M and 11.8 parts by weight of a pest control agent holding body master batch were kneaded using a Banbury mixer to prepare a resin composition for filaments. There was no stickiness of the resin composition.

3. Filament Production / Bleedability Evaluation As described in Example 1, filament production / bleedability evaluation was performed. The cumulative bleed amount after 7 days of this filament was 1.47 mg / g.

Claims (2)

In a resin composition containing high-density polyethylene, a pest control agent and synthetic silica,
The density of the high density polyethylene is 935 to 965 kg / m ³ , and the MFR is 0.1 to 6 g / 10 min.
The synthetic silica has an average pore radius of 0.040 to 0.105 μm,
100 parts by weight of high density polyethylene and 100 parts by weight of high density polyethylene,
A resin composition for filaments containing 0.1 to 10 parts by weight of a pest control agent and 0.1 to 10 parts by weight of synthetic silica.   A filament comprising the resin composition for filaments according to claim 1.