JP2008303348A - Manufacturing method of resin composition containing insect pest control agent and manufacturing method of filament - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a resin composition that is reduced in the frequency of occurrence of the filament failure generated upon forming into the filament and to provide a method of manufacturing the filament by using the resin composition manufactured by the above method. <P>SOLUTION: The manufacturing method of the resin composition containing an insect pest control agent comprises melting/mixing 100 pts.wt. of a polyethylene resin, 0.1-100 pts.wt. of a support containing the insect pest control agent and 0.01-10 pts.wt. of an antioxidant at a temperature of 180-260°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a pest control agent-containing resin composition and a method for producing a filament.

  A resin composition obtained by mixing a pest control agent and a polyethylene resin is processed into various molded products and used as a material for controlling pests such as mites, lice, mosquitoes and flies. For example, Patent Document 1 proposes a resin composition in which a pest control agent and linear low density polyethylene are mixed. Patent Document 2 proposes a resin composition in which a pest control agent, low density polyethylene and high density polyethylene are mixed.

JP-A-6-315332 JP-A-8-302080

In the production of a resin composition in which a pest control agent and a polyethylene resin are mixed, the pest control agent and, if necessary, other additives are mixed by mixing the carrier, the pest control agent and other additives as required. A pest control agent-containing carrier supported on a carrier may be prepared in advance, and the pest control agent-containing carrier and a polyethylene resin may be mixed. However, when a resin composition produced by a conventional production method having a step of mixing a pest control agent-containing carrier and a polyethylene resin is formed into a filament, the filament may be cut. The filament moldability was not fully satisfactory.
Under such circumstances, the problem to be solved by the present invention is to provide a method for producing a resin composition in which the frequency of occurrence of filament cutting generated when forming into a filament is reduced, and the resin produced by the method. It is to provide a method for producing a filament using the composition.

  That is, in the first aspect of the present invention, 100 parts by weight of a polyethylene resin, 0.1 to 100 parts by weight of a pest control-containing carrier and 0.01 to 10 parts by weight of an antioxidant are melted at a temperature of 160 to 300 ° C. The present invention relates to a method for producing a pest control agent-containing resin composition to be mixed.

  The second of the present invention is a resin composition obtained by melt-mixing a polyethylene resin and a resin composition produced by the above production method at a temperature of 180 to 260 ° C., or a resin produced by the above production method. The present invention relates to a method for producing a filament for melt spinning a composition.

  According to the present invention, there are provided a method for producing a resin composition with a reduced frequency of occurrence of filament cutting that occurs when forming into a filament, and a method for producing a filament using the resin composition produced by the method. can do.

  The pest control agent-containing carrier is produced by mixing the pest control agent and the carrier. Examples of the pest control agents include compounds having pest control properties such as insecticides, insect growth control agents and repellents.

  Examples of the insecticide include pyrethroid compounds, organophosphorus compounds, carbamate compounds, and phenylpyrazole compounds. Examples of pyrethroid compounds include permethrin, allethrin, d-arethrin, dd-arethrin, d-tetramethrin, prareslin, cyphenothrin, d-phenothrin, d-resmethrin, empentrin, fenvalerate, esfenvalerate, fenpropraslin, cyhalothrin, Cyfluthrin, etofenprox, traromesrin, esbioslin, benfluthrin, terrareslin, deltamethrin, cypermethrin, phenothrin, tefluthrin, bifenthrin, cyfluthrin, ciphenothrin, cypermethrin, alpha cypermethrin, etc. , Nared, fenthion, cyanophos, chloropyrifos, diazinon, calclofos, salicy Emissions, diazinon and the like, as the carbamate compound, methoxy diazo down, 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. 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 the pyrethroid compound having a vapor pressure of less than 1 × 10 ⁻⁶ mmHg at 25 ° C. include resmethrin and permethrin.

  As the carrier, one that can carry a pest control agent is used, and examples thereof include silica compounds, zeolites, viscosity minerals, metal oxides, mica, hydrotalcites, and organic carriers. Silica compounds include amorphous silica and crystalline silica, and examples thereof include powdered silicic acid, finely powdered silicic acid, acid clay, diatomaceous earth, quartz, and white carbon. Examples of zeolites include A-type zeolite and mordenite, and examples of viscous minerals include montmorillonite, saponite, beidellite, bentonite, kaolinite, halloysite, nacrite, decait, anoxite, illite, and sericite. Examples of metal oxides include zinc oxide, magnesium oxide, aluminum oxide, iron oxide, copper oxide, and titanium oxide. Examples of mica include mica and vermiculite. Examples of hydrotalcites include hydrotalcite. Sites, smectites, etc., and organic carriers include charcoal (charcoal, peat, grass charcoal, etc.), polymer beads (microcrystalline cellulose, polystyrene beads, acrylate beads, methacrylate esters, polyvinyl alcohol beads) etc) And their cross-linked polymer beads and the like. Other examples include pearlite, gypsum, ceramics, and volcanic rocks.

  As the carrier, an amorphous inorganic compound is preferable, and amorphous silica is more preferable.

  In mixing the carrier and the pest control agent, the amount of the carrier mixed is usually 10 to 400 parts by weight per 100 parts by weight of the pest control agent.

  In addition, in the mixing of the carrier and the pest control agent, other additives may be mixed as necessary.

  Examples of the polyethylene resin for melting and mixing the pest control-containing carrier include high-pressure method low-density polyethylene, high-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene, and these may be used alone, Two or more kinds may be used in combination.

  High pressure method As a method for producing low density polyethylene, a method of polymerizing ethylene with a radical generator under high temperature and high pressure is used.

  Examples of radical generators include di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl-peroxy-2-ethylhexanate, dicumyl peroxide, t-butyl peroxyisopropyl carbonate, and t-butyl peroxide. Examples thereof include organic peroxides such as oxybenzoate, di-t-amyl peroxide, cumyl hydroperoxide, and t-butyl peroxybivalate, and oxygen.

  As a method for producing high-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene, solution polymerization method, slurry using known olefin polymerization catalysts such as Ziegler-Natta catalyst, chromium catalyst, metallocene catalyst, etc. Examples thereof include a production method by a known polymerization method such as a polymerization method, a gas phase polymerization method, and a high-pressure ion 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 a halo alcoholate of titanium is supported on a magnesium compound and an organometallic compound as a cocatalyst ( 2) A catalyst comprising an organometallic compound which is a coprecipitate of a magnesium compound and a titanium compound or a eutectic and a cocatalyst.

  Examples of the chromium catalyst include a catalyst composed of a component in which a chromium compound is supported on silica or silica-alumina, 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-type 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 Catalysts obtained by supporting or impregnating inorganic particulate compounds such as O ₃ and particulate polymers such as olefin polymers such as ethylene and styrene.

  The melt flow rate (MFR) of the polyethylene resin is usually 0.1 to 50 g / 10 minutes. If the MFR is too high, the frequency of filament breakage may increase. The MFR is preferably 40 g / 10 min or less, more preferably 30 g / 10 min or less. The MFR is preferably 0.3 g / 10 min or more, more preferably 0.5 g / 10 min or more, from the viewpoint of reducing the motor load of the extruder during melt mixing. 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 density of the polyethylene resin is usually 900 to 965 kg / m ³ . It said seal degree, in view of enhancing the pest control of the filaments, preferably 905 kg / m ³ or more, more preferably 910 kg / m ³ or more. The density is preferably 960 kg / m ³ or less, more preferably 955 kg / m ³ or less, from the viewpoint of further reducing the occurrence frequency of filament cutting. 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 as described in JISK6760-1995.

  As the antioxidant, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or the like is used.

  Examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol (BHT) and n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate (trade name Irganox 1076, manufactured by Ciba Specialty Chemicals), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name Irganox 1010, manufactured by Ciba Specialty Chemicals) 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name Irganox 3114, manufactured by Ciba Specialty Chemicals), 1,3,5-trimethyl-2,4, 6-Tris (3,5-di-tert-butyl-4-hydroxybenzine ) Benzene, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10- And tetraoxaspiro [5,5] undecane (trade name Sumilizer GA80, manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of phosphorus antioxidants include distearyl pentaerythritol diphosphite (trade name ADK STAB PEP8), tris (2,4-di-tert-butylphenyl) phosphite (trade name Irgafos 168, manufactured by Ciba Specialty Chemicals). Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphonite (trade name Sandostab P-EPQ , Manufactured by Clariant Shapin Co., Ltd.), bis (2-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and the like.

  Examples of the antioxidant having both a phenol structure and a phosphorus structure include 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10 tetra-tert-butyldibenz. [D, f] [1, 3, 2] -Dioxaphosphabin (trade name Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  Examples of the sulfur-based antioxidant include 4,4′-thiobis (3-methyl-6-tert-butylphenol) (trade name Sumilizer WXR, manufactured by Sumitomo Chemical Co., Ltd.), 2,2-thiobis- (4-methyl- 6-tert-butylphenol) (trade name IRGANOX 1081, manufactured by Ciba Specialty Chemical Co., Ltd.).

  Examples of other antioxidants include vitamin E and vitamin A.

  The antioxidant is preferably an antioxidant having a phenol structure, more preferably a phenolic antioxidant, and still more preferably phenyl having 1 to 2 t-butyl groups and one hydroxy group. Propionic acid ester having a group, most preferably an ester of propionic acid having a phenyl group having 1 to 2 t-butyl groups and one hydroxy group and an alcohol having 2 or more carbon atoms.

  In the melt mixing of the polyethylene-based resin, the pest control-containing carrier and the antioxidant, the amount of the pest-control-agent-containing carrier is usually 0.1 to 100 parts by weight per 100 parts by weight of the polyethylene resin. The mixing amount of the agent is usually 0.01 to 10 parts by weight per 100 parts by weight of the polyethylene resin. When the resin composition after mixing is the main raw material for melt spinning, the amount of the pest control-containing carrier is preferably 0.1 to 20 parts by weight per 100 parts by weight of the polyethylene resin, and the antioxidant The mixing amount of the agent is preferably 0.01 to 1 part by weight per 100 parts by weight of the polyethylene resin. Moreover, when the resin composition after mixing is a pest control agent master batch, the mixing amount of the pest control agent-containing carrier is preferably 5 to 100 parts by weight per 100 parts by weight of the polyethylene-based resin. The mixing amount is preferably 0.03 to 10 parts by weight per 100 parts by weight of the polyethylene resin.

  When the resin composition is for filaments, the content of the carrier in the resin composition (only the carrier in the case of the pest control agent-containing carrier) is from the viewpoint of increasing mechanical strength, per 100 parts by weight of the polyethylene resin, Preferably it is 50 weight part or less, More preferably, it is 30 weight part or less. Further, the content is preferably 0.3 parts by weight or more, more preferably 0.6 parts by weight or more from the viewpoint of improving the pest control performance.

  In the melt mixing of the polyethylene-based resin, the pest control-containing carrier and the antioxidant, other components may be mixed as necessary. For example, you may mix | blend the compound which has a role which raises the effect of pest control property. Examples of the compound include piperonyl butoxide, MGK264, octachlorodipropyl ether and the like. Further, additives such as anti-blocking agents, fillers, lubricants, antistatic agents, weathering stabilizers, pigments, processability improvers, metal soaps and the like may be blended, and these additives may be used in combination of two or more. Good.

  The temperature at which the polyethylene-based resin, the pest control-containing carrier and the antioxidant are melt-mixed is usually 160 to 300 ° C, preferably 180 to 260 ° C.

  The melt mixing of the polyethylene-based resin, the pest control-containing carrier and the antioxidant can be performed by a known mixer such as a twin screw extruder, a Banbury mixer, a roll kneader or the like.

  A resin composition obtained by melt-mixing a polyethylene-based resin, a pest control-containing carrier and an antioxidant is used as a main raw material for a melt spinning raw material, and is formed into a filament. In addition, the resin composition is used as a pest control master batch, melted and mixed with the above-described polyethylene resin, and then formed into a filament.

  The content of the pest control agent-containing carrier in the resin composition obtained by melt-mixing the pest control master batch and the above-mentioned polyethylene resin is the total amount of the polyethylene resin (mixed with the polyethylene resin and the master batch in the master batch The total amount of polyethylene resin) is preferably 1 to 20 parts by weight per 100 parts by weight, and the antioxidant content is the total amount of polyethylene resin (polyethylene resin mixed with the polyethylene resin and master batch in the master batch) The total amount of resin) is preferably 0.05 to 1 part by weight per 100 parts by weight.

  The temperature at which the pest control agent master batch and the above-mentioned polyethylene resin are melt-mixed is usually 160 to 300 ° C, preferably 180 to 260 ° C. Melt mixing can be performed by a known mixer, for example, a twin screw extruder, a Banbury mixer, a roll kneader or the like.

  Filaments are manufactured by melt spinning. For example, the resin composition is melted using an extruder or the like, passed through a gear pump, etc., melted and extruded from a die / nozzle, the extruded resin composition is taken into a strand shape, and the strand-shaped resin composition There is a method in which the material is cooled by using a cooling medium such as water or air to perform spinning, and then subjected to treatment such as heat stretching, heat treatment, and oil coating as necessary, and then winding.

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

  Monofilament uses include nets and nets such as mosquito nets, screen doors and insect nets; ropes; threads; filters, etc. Multifilament uses include ropes, nets, carpets, non-woven fabrics, filters, shoes, clothing, etc. Is given. In particular, applications that require pest control, such as mosquito nets, screen doors, insect nets, filters, carpets, shoes, and clothing are suitable.

  Examples of insects targeted for filament control include arthropods such as spiders, mites, and insects. Further examples will be described as follows. Examples of the staghorn rope include acarid mites (Acarina), citrus mite, mite mite, etc .; a spider (Araneae), a yellow spider, and the like. 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; , Black cockroaches, cockroaches, cockroaches, etc.; Yamato termites, termites, termites, etc.; Ants that belong to the order of Psocoptera, etc.; Cat lice, etc .; body lice, pheasants, and human lice belonging to the order of Anoplura; leafhoppers, leafhoppers, leafhoppers, aphids, leafworms belonging to the order of Hemiptera Mi, Kusagi beetle, etc .; Coleoptera, cutworm beetle, cucumber weevil, weevil, flathead beetle, Nagaryo hornworm, 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) Density (Unit: kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The measurement sample piece was annealed according to JIS K6760-1995 and used for measurement.

Example 1
(1) Preparation of a pest control-containing carrier Permethrin (trade name Exmin, manufactured by Sumitomo Chemical Co., Ltd.) 51 parts by weight is referred to as antioxidant 2,6-di-t-butyl-4-methylphenol (hereinafter referred to as AO-1). .) 1.5 parts by weight were dissolved. Next, 52.5 parts by weight of a mixture of permethrin and AO-1 and 47.5 parts by weight of amorphous silica (trade name porous silica manufactured by Suzuki Yushi) (93.1 parts by weight per 100 parts by weight of permethrin) The mixture was stirred and mixed to prepare a pest control agent-containing carrier.

(2) Preparation of Pest Control Master Batch 60.15 parts by weight of high-pressure low-density polyethylene (Sumitomo Chemical Sumikasen CE5502) (hereinafter referred to as LD) and antioxidant (AO-1) 0. 05 parts by weight (0.08 parts by weight per 100 parts by weight of LD), 31 parts by weight of a pest control carrier-containing carrier (51.54 parts by weight per 100 parts by weight of LD), 5 parts by weight of zinc stearate, A pest control agent master batch was prepared by melt-kneading 4.52 parts by weight with a twin screw extruder at a temperature of 200 ° C.

(3) Preparation of Filament Molding Resin Composition 100 parts by weight of high-density polyethylene (manufactured by Prime Polymer, trade name: Hi-Xex 5000S; MFR = 0.8 g / 10 min, density = 948 kg / m ³ ) and a pest control agent master 16.5 parts by weight of the batch and 7 parts by weight of zinc stearate were melt-kneaded at a temperature of 260 ° C. using a twin screw extruder to prepare a resin composition for filament molding.

(4) Manufacture of filaments Using a 50 mmφ extruder with a 0.8 mmφ-150 hole die, the filament molding resin composition was extruded at a discharge rate of 20 kg / hr, a die set temperature of 190 ° C., and a line speed of 14 m / min. The sample was taken out, passed through a heated water bath at 112 m / min, and formed into a 200 denier monofilament. The filament cutting frequency during molding was 2.7 per hour.

Comparative Example 1
Prepare a resin composition for forming a filament according to the method of Example 1 except that when the pest control master batch is prepared, the high-pressure low-density polyethylene pellets are 60.2 parts by weight and no antioxidant is added. did. The obtained resin composition for forming a filament was formed into a monofilament in the same manner as in Example 1. The filament cutting frequency during molding was 5.1 per hour.

Example 2
When preparing the insect pest control master batch, the high-pressure low-density polyethylene pellets were 60.08 parts by weight, and instead of the antioxidant AO-1, pentaerythrityl-tetrakis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate] (trade name Irganox 1010, manufactured by Ciba Specialty Chemicals; hereinafter referred to as AO-2) 0.12 parts by weight, except for 0.12 parts by weight Resin for filament molding according to the method of Example 1 A composition was prepared. The obtained resin composition for forming a filament was formed into a monofilament in the same manner as in Example 1. The filament cutting frequency during molding was 2.5 per hour.

Example 3
In preparing the pest control master batch, the high-pressure low-density polyethylene pellets were changed to 60.11 parts by weight, and instead of the antioxidant AO-1, n-octadecyl-3- (3,5-di-t- A resin composition for forming a filament according to the method of Example 1 except that 0.09 part by weight of butyl-4-hydroxyphenyl) propionate (trade name Irganox 1076 manufactured by Ciba Specialty Chemicals Co., Ltd .; hereinafter referred to as AO-3) was used. Prepared. The obtained resin composition for forming a filament was formed into a monofilament in the same manner as in Example 1. The filament cutting frequency during molding was 0.8 per hour.

Claims (2)

  A pest control agent-containing resin composition in which 100 parts by weight of a polyethylene resin, 0.1 to 100 parts by weight of a pest control agent-containing carrier and 0.01 to 10 parts by weight of an antioxidant are melt-mixed at a temperature of 180 to 260 ° C. Manufacturing method.   A resin composition obtained by melt-mixing a polyethylene resin and the resin composition produced by the production method according to claim 1 at a temperature of 180 to 260 ° C, or produced by the production method according to claim 1. For producing a filament by melt spinning the prepared resin composition.