CN101511191B - Method for preparing insect-repellent compound-containing resin pellet - Google Patents
Method for preparing insect-repellent compound-containing resin pellet Download PDFInfo
- Publication number
- CN101511191B CN101511191B CN2007800336044A CN200780033604A CN101511191B CN 101511191 B CN101511191 B CN 101511191B CN 2007800336044 A CN2007800336044 A CN 2007800336044A CN 200780033604 A CN200780033604 A CN 200780033604A CN 101511191 B CN101511191 B CN 101511191B
- Authority
- CN
- China
- Prior art keywords
- insect
- repellent compound
- resin
- ethene
- repellent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Abstract
The invention provides a method for preparing a resin pellet which contains an insect-repellent compound at a desired concentration, by reducing the loss of the insect-repellent compound in the course of preparing the insect-repellent compound-containing resin pellet. The invention relates to a method for preparing an insect-repellent compound-containing resin pellet, said method comprising the steps of mixing porous particles impregnated with an insect-repellent compound with an ethylene based resin satisfying the following condition (1) so that the ratio of said porous particles impregnated with said insect-repellent compound/said ethylene based resin is 20 to 60 wt.%/40 to 80 wt.%, melt-kneading the resulting composition with a twin-screw extruder, and extruding the composition as a strand, and cutting the strand into pellets of the insect-repellent compound-containing resin, wherein said condition (1) of said ethylene based resin is that the ratio of (eta1/eta2) is from 1.8 inclusive to 3 inclusive, in which eta1 is the melt viscosity of the ethylene based resin at 200 DEG C and at a shear rate of 120 sec<-1>, measured with a capillary rheometer, and eta2 is the melt viscosity of the ethylene based resin at 200 DEG C and at a shear rate of 120 sec<-1>, measured with a capillary rheometer.
Description
Technical field
The present invention relates to the preparation method of the resin pellet of insect-repellent compound-containing.
Background of invention
The resin combination of the insect-repellent compound-containing that is obtained by the kneading of insect-repellent compound and resin can be shaped to required shape, and this moulded products is used for multiple field, because it can keep long disinsectization performance.For example; JP-A-4-65509/1992 discloses the method that is obtained fiber by the moulding of the resin combination of insect-repellent compound-containing; Wherein use the Banbury mixing machine that this insect-repellent compound and this resin are mediated to form the resin pellet of insect-repellent compound-containing; With this Banbury mixing machine it is further mediated to form pill with resin, use it for melt-spun (referring to JP-A-4-65509/1992) then.
Summary of the invention
Yet; Use the traditional preparation process method of the insect-repellent compound-containing resin pellet of Banbury mixing machine to have following problem: this insect-repellent compound decomposes or volatilization in the preparation process of this pill, and this makes the resin pellet that is difficult to obtain contain the insect-repellent compound of desired concn.
Therefore the purpose of this invention is to provide the method for preparing the resin pellet of the insect-repellent compound that comprises desired concn through the loss of this insect-repellent compound in the preparation process that is reduced in this pill.
That is, the invention provides the preparation method of the resin pellet of insect-repellent compound-containing, this method may further comprise the steps:
The resin based on ethene of the porous particle that is impregnated with insect-repellent compound with meet the following conditions (1) mixed mutually, is 20～60wt%/40～80wt% so that this is impregnated with the porous particle of insect-repellent compound/based on the ratio of the resin of ethene,
With double screw extruder with the resultant composition melt kneading, and with said composition extrude as strand and
This strand is cut into the resin pellet of insect-repellent compound-containing,
Wherein this condition (1) based on the resin of ethene is (η
1/ η
2) ratio be 1.8 (comprising end points)～3 (comprising end points), wherein η
1For this is 120sec based on the resin of ethene 200 ℃ and shear rate
-1The time melt viscosity, measure η with capillary rheometer
2For this is 1200sec based on the resin of ethene 200 ℃ and shear rate
-1The time melt viscosity.
According to method of the present invention, can be reduced in the loss of this insect-repellent compound in the preparation process of this pill, make the resin pellet that can prepare the insect-repellent compound that comprises desired concn.
The description of preferred implementation
In the method for the invention, use is based on the resin and the porous particle that is impregnated with insect-repellent compound of ethene.
The instance of insect-repellent compound comprises pyrethroid compound, for example permethrin (permethrin), cyphenothrin (cyphenothrin), d-phenothrin (d-phenothrin), 4-resmethrin (4-resmethrin), sumicidin (fenvalerate), fenpropathrin (fenpropathrin), ether chrysanthemum ester (etofenprox), tralomethrin (tralomethrin), third Flumethrin (profluthrin) and methoxy benzyl Flumethrin (metofluthrin).In these insect-repellent compounds, preferably use in the time of 25 ℃ to be the compound of liquid state.Also can use the insect-repellent compound of non-pyrethroid compound.In the present invention, the insect-repellent compound of single kind be can use, two kinds or more kinds of insect-repellent compound perhaps can be used in combination.
Although silica is used in not special restriction usually in the selection of the kind that is used for porous particle of the present invention.Use with porous particle of too small average grain diameter causes the reunion of this porous particle easily, and this makes and be difficult to form uniform dispersion, and makes that very fine particle flies away easily in the preparation process.On the other hand, the use with porous particle of excessive average grain diameter causes the surface roughening of moulded products when being used for moulding, or the fiber of easy fracture is provided.Therefore, the average grain diameter of this porous particle is generally 0.03～40 μ m, preferred 0.1～20 μ m.
In the present invention, use the porous particle that is impregnated with insect-repellent compound.Therefore, by according to JIS K 5101-13-1, the test method of pigment, the oil absorption of this porous particle that the pure linseed oil method of the 13rd part is measured is preferably 100～180ml/100g.When the oil absorption of this porous particle is too small, be difficult to make the insect-repellent compound of this porous particle dipping aequum.On the other hand, when its oil absorption was excessive, the absorption of insect-repellent compound became strong, made to be difficult to discharge this insect-repellent compound.Therefore resulting moulded products can not have required anthelmintic action.
The ratio of this porous particle and this insect-repellent compound can suitably be selected according to the oil absorption of this porous particle.Usually, the insect-repellent compound of per 100 weight portions uses the porous particle of 50～200 weight portions.
Although not restriction in the selection of the method for flooding this porous particle with this insect-repellent compound, preferably insect-repellent compound or the solution of insect-repellent compound in solvent with liquid state adds in the porous particle in the stirring gradually.
The instance based on the resin of ethene that is used for the present invention comprises that density is 0.850g/cm
3(comprising end points)～less than 0.930g/cm
3Low density polyethylene (LDPE), LLDPE, density be 0.930g/cm
3(comprising end points)～less than 0.942g/cm
3Medium density polyethylene, density be 0.942g/cm
3Or higher high density polyethylene (HDPE) and ethene and be selected from vinyl carboxylate and the copolymer of at least a monomer of esters of unsaturated carboxylic acids.These copolymers comprise ethene-vinyl carboxylate copolymer and ethene-unsaturated carboxylic acid ester copolymer.This ethene-vinyl carboxylate copolymer can be vinyl-vinyl acetate copolymer (or EVA).This ethene-unsaturated carboxylic acid ester copolymer can be (or EEA) such as ethylene-methyl methacrylate methyl terpolymer (or EMMA), ethylene-methyl acrylate copolymer (or EMA), ethylene-ethyl acrylate copolymers etc.Can use these based on any of the resin of ethene separately, perhaps can be used in combination two kinds or more kinds of resin based on ethene.
The resin based on ethene that is used for the present invention meets the following conditions: i.e. (η
1/ η
2) ratio be 1.8 (comprising end points)～3 (comprising end points), wherein η
1Should be 120sec 200 ℃ and shear rate based on the resin of ethene for what use capillary rheometer determining
-1The time melt viscosity, η
2For it is 1200sec 200 ℃ and shear rate
-1The time melt viscosity.When the porous particle that will be impregnated with insect-repellent compound with double screw extruder and this resin melt kneading, the loss of this insect-repellent compound can reduce, and can prepare the resin pellet of the insect-repellent compound that comprises desired concn.Mediate this temperature with this extruder and be generally about 150～about 210 ℃ based on the resin of ethene.When using its η
1/ η
2Surpass 3 based on the resin of ethene the time, should in this extruder, have higher temperature based on resin of ethene, this makes the pill of the insect-repellent compound that can not obtain comprising desired concn.In this, the shear rate is here represented the apparent shear rate when measuring with capillary rheometer, found.
The porous particle that is impregnated with insect-repellent compound is as follows with this mixing ratio based on the resin of ethene: when this resin based on ethene is 100wt% with this total amount that is impregnated with the porous particle of insect-repellent compound; This is impregnated with the porous particle of insect-repellent compound/based on the ratio of the resin of ethene is 20～60wt%/40～80wt%, preferred 30～60wt%/40～70wt%.When the percentage of the porous particle that is impregnated with insect-repellent compound during, can not obtain to comprise the pill of the insect-repellent compound of high concentration less than 20wt%.On the other hand, when the percentage of identical porous particle surpasses 60wt%, form pill and become impossible.
When mixing thermoplastic resin with the formation pill with various additives traditionally, at first this resin and additive are mixed with banbury mixers, then this mixture is formed pill.Yet the use of banbury mixers increases the loss of insect-repellent compound easily, because insect-repellent compound adheres on the inwall of this device or from this mixer, leaks into the outside.Simultaneously, use single screw extrusion machine to replace banbury mixers to cause the dispersion of porous particle insufficient.In order to solve these shortcomings, in the present invention, use double screw extruder will be somebody's turn to do and mediate with the porous particle that is impregnated with insect-repellent compound based on the resin of ethene.Used double screw extruder is restriction not.Yet, use its L/D to be about double screw extruder of 20～about 60 usually.Preferably, the L/D of the spiro rod section in kneading zone is 0.5～1.0.In addition, in order to suppress to mediate the heat of giving birth in the zone, it is better not using the spiro rod section that reverses.Kneading temperature in the double screw extruder is generally 150～210 ℃.
In the present invention; This is impregnated with the porous particle of insect-repellent compound and during based on the resin of ethene when melt kneading in double screw extruder, can randomly add antioxidant, UV absorbent, antistatic additive, lubricant, antiblocking agent, pigment, nucleator, metallic soap, antibiotic and antimycotic component etc.
Will be with double screw extruder, and it is extruded as its strand based on the resin of ethene and the mixture melt kneading that is impregnated with the porous particle of insect-repellent compound, then with its cutting to obtain the pill of insect-repellent compound-containing resin.Usually this strand that will from this extruder, extrude makes its cooling through cooling water, cuts with granulator then.
According to the preparation method of the resin pellet of insect-repellent compound-containing of the present invention, can be reduced in the loss of insect-repellent compound in the preparation process of this pill.Therefore method of the present invention is applicable to that preparation comprises the pill of the insect-repellent compound of high concentration.For example, method of the present invention can prepare the pill that comprises 15wt% or more insect-repellent compounds, is reduced in the loss of this insect-repellent compound in the preparation process simultaneously.Can be directly formed to required shape although comprise the insect-repellent compound-containing resin pellet of the insect-repellent compound of high concentration like this, these pill particularly suitables are made the masterbatch of insect-repellent compound.Special, the resin pellet mixing with resin and this insect-repellent compound-containing makes that the concentration of this insect-repellent compound can be desirable value after mixing, and resulting mixture is used for moulding.The shape of this forming method and moulded products is restriction not.For example, with this mixture film extrusion so that insect pest-repellent film to be provided; With this mixture injection moulding to be provided for expelling parasite necklace or the ear tag of animal; With this mixture melt-spun so that insect-repellent fiber to be provided; And further this insect-repellent fiber is weaved or woven so that mosquito net etc. to be provided.
Embodiment
To the present invention be described in more detail through the mode of embodiment below, embodiment never should be interpreted as the scope of the present invention that limits.Carry out as follows embodiment and Comparative Examples insect-repellent compound analysis and based on the mensuration of the melt viscosity of the resin of ethene.
(1) insect-repellent compound Determination on content
Sample (about 0.25g) is put into boiling flask also accurately weighs.Mark liquid (di-n-octyl phthalate/xylol of 6000ppm) (5ml) adds xylol (45ml) then in adding then.This flask is fixed on the reflux, at 75 ℃ with this sample extraction 2 hours.With the extract cooling, and use gas chromatographic analysis.
Analytical conditions for gas chromatography is following:
Detector: flame ionization detector
Post: DB-17 capillary column
Column temperature: 225 ℃
Gasification chamber temperature: 270 ℃
Detector temperature: 280 ℃
(3) mensuration of melt viscosity
According to JIS K 7199 (flowabilities of plastics-uses capillary and trough of belt mould rheometer mensuration plastics), under following condition, carry out mensuration with capillary rheometer based on the melt viscosity of the resin of ethene with the capillary rheometer method:
Instrument: capillary rheometer, by Toyo Seiki Seisaku-sho, the Capillograph 1B that Ltd. makes
Orifice area: internal diameter 1mm, long 40mm
L/D：40
Measure temperature: 200 ℃
Melt viscosity: the mensuration apparent shear rate is 120sec
-1The time melt viscosity η
1With apparent shear rate be 1200sec
-1The time melt viscosity η
2(unit is Pas).
Embodiment 1
(average grain diameter is the porous silica of 12 μ m with porous particle with mixer; Oil absorption (JISK 5101-13-1; The test method of pigment; The 13rd part: oil absorption; The 1st chapter: pure linseed oil method)=130ml/100g) (35.5 weight portion) and mix as the permethrin (38.1 weight portion) of insect-repellent compound, further add BHT (1.1 weight portion), zinc stearate (21.7 weight portion) and blue pigment (ultramarine violet) (3.6 weight portion) therein to obtain the mixture of insect-repellent compound-containing.
Mixture (41.5 weight portion) and LLDPE (LLDPE) (Sumitomo Chemical Company, the SumikatheneL GA807 of Limited preparation with this insect-repellent compound-containing; Density=0.913g/cm
3, η
1=280, η
2=140, η
1/ η
2=2) (58.5 weight portion) mixes, with double screw extruder under 200 ℃ melt kneading district temperature with this mixture melt kneading, in 200 ℃ of die heads that heat down, it is extruded as its strand then.This strand of extruding is cooled off it through bosh, with granulator this strand is cut to obtain being of a size of the pill of the long insect-repellent compound-containing resin of Φ 2mm * 3mm then.Measure the insect-repellent compound content in the pill, be found to be 15.8wt%.The theoretical content of insect-repellent compound is 15.8wt% in the pill that is calculated by the addition of raw material, has confirmed that therefore this insect-repellent compound is included in this pill according to this prescription.
Comparative Examples 1
Repeat embodiment 1, only be to use high density polyethylene (HDPE) (HDPE) (MITSUICHEMICALS, the HI-ZEX 5000S of INC. preparation; Density=0.950g/cm
3, η
1=1900, η
2=265, η
1/ η
2=7.2) replace LLDPE.Resulting mixture is extruded, and the melt kneading district temperature of this double screw extruder is set at 200 ℃, and its die head temperature also is 200 ℃.Yet it is very violent to generate heat, and this temperature is elevated to 300 ℃.This strand of extruding is cooled off it through bosh.Then with the pill of this strand of granulator cutting with the resin that obtains insect-repellent compound-containing.This pill comprises a lot of bubbles.Infer that this insect-repellent compound spumes and caused this foaming.The insect-repellent compound content of measuring in this pill is 14.7wt%.
Main embodiment of the present invention and preferred embodiment have been listed below.
The preparation method of the resin pellet of insect-repellent compound-containing, this method may further comprise the steps:
The resin based on ethene of the porous particle that is impregnated with insect-repellent compound with meet the following conditions (1) mixed mutually, is 20～60wt%/40～80wt% so that this is impregnated with the porous particle of said insect-repellent compound/said based on the ratio of the resin of ethene,
With double screw extruder with the resultant composition melt kneading, and with said composition extrude as strand and
This strand is cut into the resin pellet of insect-repellent compound-containing,
Wherein this said condition (1) based on the resin of ethene is (η
1/ η
2) ratio be 1.8 (comprising end points)～3 (comprising end points), wherein η
1For this is 120sec based on the resin of ethene 200 ℃ and shear rate
-1The time melt viscosity, measure η with capillary rheometer
2For this is 1200sec based on the resin of ethene 200 ℃ and shear rate
-1The time melt viscosity.
This application requires the Paris Convention priority of japanese patent application No. 2006-245255, and its full content is introduced here by reference.
Claims (1)
1. the preparation method of the resin pellet of insect-repellent compound-containing said method comprising the steps of:
The resin based on ethene of the porous particle that is impregnated with insect-repellent compound with meet the following conditions (1) mixed mutually, so that the said porous particle that is impregnated with said insect-repellent compound/ratio of said resin based on ethene is 20～6wt%/40～80wt%,
With double screw extruder with the resultant composition melt kneading, and with said composition extrude as strand and
Said strand is cut into the resin pellet of insect-repellent compound-containing,
The said condition (1) of wherein said resin based on ethene is η
1/ η
2Ratio be 1.8～3, all comprise end points, wherein η
1For this is 120sec based on the resin of ethene 200 ℃ and shear rate
-1The time melt viscosity, measure η with capillary rheometer
2For this is 1200sec based on the resin of ethene 200 ℃ and shear rate
-1The time melt viscosity.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP245255/2006 | 2006-09-11 | ||
| JP2006245255 | 2006-09-11 | ||
| PCT/JP2007/068003 WO2008032840A2 (en) | 2006-09-11 | 2007-09-10 | Method for preparing insect-repellent compound-containing resin pellet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101511191A CN101511191A (en) | 2009-08-19 |
| CN101511191B true CN101511191B (en) | 2012-10-10 |
Family
ID=39184218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800336044A Expired - Fee Related CN101511191B (en) | 2006-09-11 | 2007-09-10 | Method for preparing insect-repellent compound-containing resin pellet |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101511191B (en) |
| WO (1) | WO2008032840A2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110432264A (en) * | 2019-08-07 | 2019-11-12 | 华南农业大学 | A kind of medicament-carrying nano-microsphere, slow releasing pharmaceutical expelling parasite Pet neck ring and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4680328A (en) * | 1984-11-29 | 1987-07-14 | The Dow Chemical Company | Insect resistant polyethylene composition suitable for wire and cable applications |
| CN1233149A (en) * | 1996-08-19 | 1999-10-27 | 巴特勒记忆研究所 | Method of making controlled release devices |
| US6852328B1 (en) * | 1989-09-01 | 2005-02-08 | Battelle Memorial Institute K1-53 | Method and device for protection of wooden objects proximate soil from pest invasion |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58113102A (en) * | 1981-12-26 | 1983-07-05 | Earth Chem Corp Ltd | Method for slowing release of drug |
| JPH0465509A (en) * | 1990-06-29 | 1992-03-02 | Sumitomo Chem Co Ltd | Production of moth-proofing fiber |
| JPH08163950A (en) * | 1994-05-19 | 1996-06-25 | Tokyo Ink Kk | Resin net for controlling pest insect |
| JP3360532B2 (en) * | 1996-06-12 | 2002-12-24 | 住友ベークライト株式会社 | Thermoforming resin composition and sheet |
| US20020165297A1 (en) * | 2001-02-02 | 2002-11-07 | The 54 Group, Ltd. | Polymeric resins impregnated with insect repellants |
-
2007
- 2007-09-10 WO PCT/JP2007/068003 patent/WO2008032840A2/en active Application Filing
- 2007-09-10 CN CN2007800336044A patent/CN101511191B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4680328A (en) * | 1984-11-29 | 1987-07-14 | The Dow Chemical Company | Insect resistant polyethylene composition suitable for wire and cable applications |
| US6852328B1 (en) * | 1989-09-01 | 2005-02-08 | Battelle Memorial Institute K1-53 | Method and device for protection of wooden objects proximate soil from pest invasion |
| CN1233149A (en) * | 1996-08-19 | 1999-10-27 | 巴特勒记忆研究所 | Method of making controlled release devices |
Non-Patent Citations (2)
| Title |
|---|
| JP平4-65509A 1992.03.02 |
| JP特开平8-163950A 1996.06.25 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008032840A3 (en) | 2008-10-23 |
| CN101511191A (en) | 2009-08-19 |
| WO2008032840A2 (en) | 2008-03-20 |
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