CN102334474B - Small animal control resin composition - Google Patents
Small animal control resin composition Download PDFInfo
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- CN102334474B CN102334474B CN201110178926.6A CN201110178926A CN102334474B CN 102334474 B CN102334474 B CN 102334474B CN 201110178926 A CN201110178926 A CN 201110178926A CN 102334474 B CN102334474 B CN 102334474B
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Abstract
The invention provides a small animal control resin composition advantaged by low cost and good repellent performance of a small animal. The basic composition comprises (A1) an olefin resin, (B) a small animal controlling agent, and (C) a slow release auxiliary agent for the small animal controlling agent. In addition, the basic composition also comprises (A2) a polyamide resin and (A3) at least one resin material selected from (A3) maleic anhydride modified polyester, maleic anhydride modified polypropylene, maleic anhydride modified phenylethylene-ethylene-butylene segmented copolymer, and ethylene-glycidyl methacrylate copolymer, or also comprises (A4) at least a resin material selected from ethylene-vinyl carboxylate ester copolymer and ethylene-unsaturated carboxylic ester copolymer, or also comprises the polyamide resin (A2), at least one selected from the resin material (A3), and at least one selected from the resin material (A4).
Description
Technical field
The present invention relates to mixing for the small animal agent for preventing and eliminating small animal control resin composition in resin, particularly realize the means of small animal control energy and persistent improvement and cost degradation.
Background technology
In the past, as small animal control resin composition, propose to have in base resin mixing small animal agent for preventing and eliminating and dissolve keep this small animal agent for preventing and eliminating and give slow release slowly-releasing auxiliary agent and obtain composition (such as with reference to patent document 1), in base resin mixing small animal agent for preventing and eliminating and improve the composition (such as reference patent document 2) etc. that small animal agent for preventing and eliminating obtains for the affinity resin of the affinity of base resin.
The small animal control resin composition recorded in patent document 1 because in base resin the slowly-releasing auxiliary agent of mixing small animal agent for preventing and eliminating, so small animal control energy can be played for a long time.In addition, the small animal control resin composition recorded in patent document 1 is selected from resin based at least a kind of resin of polyamide and polyacetal resin, so have the intensity, warm tolerance and the chemical resistance that can be used as various structural elements because of use.On the other hand, the small animal control resin composition recorded in patent document 2 is because of the affinity resin of mixing small animal agent for preventing and eliminating in base resin, so small animal agent for preventing and eliminating can be improved for the dispersiveness of base resin and compatibility, can the higher small animal agent for preventing and eliminating conservation rate of long term maintenance.
Patent document 1: Japanese Patent Laid-Open 2000-212005 publication
Patent document 2: Japanese Patent Laid-Open 2008-206492 publication
Summary of the invention
In addition, for this small animal control resin composition, require that there is following properties evenly: to keep away quick-acting high for the rate of keeping away and avoiding of avoiding of the small animal that (a) is harmful; When () is configured as various structural elements b, the small animal agent for preventing and eliminating of ormal weight after shaping, is had rapidly to ooze out into the surface of structural elements; C () small animal agent for preventing and eliminating, from the surperficial slow releasing of structural elements, can play small animal control energy for a long time; D () can implement at low cost.In order to meet described properties, must equably and with the mixing small animal agent for preventing and eliminating of the form that can control slow release in base resin, therefore need to improve base resin and mixing in the compatibility of slowly-releasing auxiliary agent wherein.
If this is because slowly-releasing auxiliary agent is low for the compatibility of base resin, then the surface to base resin easily separated out by slowly-releasing auxiliary agent, small animal agent for preventing and eliminating can be made to separate out at short notice use up, even if the performance of above-mentioned (a) and (b) therefore can be met, the performance of above-mentioned (c) also cannot be met.In addition, in order to play small animal control energy for a long time, a large amount of small animal agent for preventing and eliminating must be added in base resin, so cost is high, also cannot meet the performance of above-mentioned (d).
But, the slowly-releasing auxiliary agent of small animal agent for preventing and eliminating is added with in the small animal control resin composition recorded in patent document 1, but do not adopt any way to improve the compatibility of base resin and slowly-releasing auxiliary agent, so according to the kind of base resin, the situation of the performance that cannot meet above-mentioned (a) ~ (d) may be there is.
On the other hand, the slowly-releasing auxiliary agent of small animal agent for preventing and eliminating is not added in the small animal control resin composition recorded in patent document 2, so namely allow to long-term (according to patent document 2 be recited as 3 months), keeping anti-termite agent as in the anti-ant sheet of goods, also cannot determine whether that anti-termite agent suitably carries out from the stripping of anti-ant sheet and plays anti-ant effect for a long time.
The invention that the present invention is actual conditions in view of described prior art and completes, its object is to provide cost low but the Inherited movement of small animal can be good small animal control resin composition.
In order to solve such technical task, the 1st kind of formation that the present invention adopts comprises: (A1) olefine kind resin, (B) small animal agent for preventing and eliminating, (C) the slowly-releasing auxiliary agent of small animal agent for preventing and eliminating, (A2) polyimide based resin, and (A3) is selected from least a kind of resin material of maleic anhydride modified polyester, maleic anhydride modified polypropylene, maleic anhydride modified styrene-ethylene-butadiene block copolymer and ethylene-methyl methacrylate glycidyl ester copolymer.
The 2nd kind of formation adopted comprises: (A1) olefine kind resin, (B) small animal agent for preventing and eliminating, (C) the slowly-releasing auxiliary agent of small animal agent for preventing and eliminating, and (A4) is selected from least a kind of resin material of ethylene-vinyl carboxylate's copolymer and ethene-unsaturated carboxylic acid ester copolymer.
The 3rd kind of formation adopted comprises: (A1) olefine kind resin, (B) small animal agent for preventing and eliminating, (C) the slowly-releasing auxiliary agent of small animal agent for preventing and eliminating, (A2) polyamide-based resin, (A3) be selected from least a kind of resin material of maleic anhydride modified polyester, maleic anhydride modified polypropylene, maleic anhydride modified styrene-ethylene-butadiene block copolymer and ethylene-methyl methacrylate glycidyl ester copolymer, and (A4) is selected from least a kind of resin material of ethylene-vinyl carboxylate's copolymer and ethene-unsaturated carboxylic acid ester copolymer.
Olefine kind resin (A1) is matrix resin small animal control resin composition being configured as structure.Slowly-releasing auxiliary agent (C) gives olefine kind resin (A1) with the reagent of the slow release of small animal agent for preventing and eliminating (B).Polyamide-based resin (A2) is the carrying resin of carrying small animal agent for preventing and eliminating (B), has the function of the maintenance dose of the small animal agent for preventing and eliminating (B) in adjustment olefine kind resin (A1).Resin material (A3) be improve polyamide-based resin (A2) for olefine kind resin (A1) compatibility help dispersion resin, have and make polyamide-based resin (A2) be scattered in function in olefine kind resin (A1) equably.In addition, resin material (A4) improves the affinity resin of small animal agent for preventing and eliminating (B) for the affinity of olefine kind resin (A1), has the function of adjustment small animal agent for preventing and eliminating (B) from the slowly-releasing amount of olefine kind resin (A1).
Olefine kind resin (A1) is low with the compatibility of slowly-releasing auxiliary agent (C), therefore slowly-releasing auxiliary agent (C) is added only by olefine kind resin (A1), the slow release of small animal agent for preventing and eliminating (B) cannot be given full play to, be difficult to obtain the high and small animal control resin molded body that product life is long of the Repellency effect of small animal.Further, also fail at present to find the slowly-releasing auxiliary agent high with the compatibility of olefine kind resin (A1).If at olefine kind resin (A1), small animal agent for preventing and eliminating (B), polyamide-based resin (A2) is added in the mixture of slowly-releasing auxiliary agent (C), then small animal agent for preventing and eliminating (B) is carried on polyamide-based resin (A2), so can reliably make the small animal agent for preventing and eliminating (B) of ormal weight remain in olefine kind resin (A1), if add resin material (A3) further in the mixture, then polyamide-based resin (A2) is improved for the compatibility of olefine kind resin (A1), so small animal agent for preventing and eliminating (B) can be made to be scattered in equably in olefine kind resin (A1).Therefore, suitably can control the stripping of small animal agent for preventing and eliminating (B) from small animal control resin composition, can while the Repellency effect needed for playing, this effect be continued for a long time.In addition, because do not need the addition exceedingly increasing small animal agent for preventing and eliminating (B), the cost degradation of small animal control resin composition can be realized.In addition, olefin resin can adopt the various manufacturing process such as injection molded or extrusion molding to be configured as various formed products, so versatility is good, and cost is low, thus can reduce the material cost of small animal control resin composition.
In addition, if add resin material (A4) in the mixture of olefine kind resin (A1), small animal agent for preventing and eliminating (B), slowly-releasing auxiliary agent (C), then small animal agent for preventing and eliminating (B) is improved for the affinity of olefine kind resin (A1), so the precipitation of small animal agent for preventing and eliminating (B) from small animal control resin composition suitably can be controlled, can while the Repellency effect needed for playing, this effect be continued for a long time.
Therefore, by adding polyamide-based resin (A2) and resin material (A3) or add resin material (A4) or add polyamide-based resin (A2), resin material (A3) and resin material (A4) in the mixture of olefine kind resin (A1), small animal agent for preventing and eliminating (B), slowly-releasing auxiliary agent (C) simultaneously, can be made into high-performance and the small animal control resin composition of low cost.
In addition, the invention is characterized in, in the small animal control resin composition of described formation, the containing ratio of (B) small animal agent for preventing and eliminating of the total amount relative to described small animal control resin composition is made to be more than 1 % by weight or 1 % by weight and less than 10 % by weight or 10 % by weight.
Because the ratio of small animal agent for preventing and eliminating shared by the manufacturing cost of small animal control resin composition is high, so the content by reducing small animal agent for preventing and eliminating, the cost degradation of small animal control resin composition can be realized.On the contrary, if the content of small animal agent for preventing and eliminating is too low, then the Repellency effect of small animal is low, and the continuation of this effect also reduces.The containing ratio describing the small animal agent for preventing and eliminating made in small animal control resin composition in patent document 1 is the technology of 5 % by weight ~ 20 % by weight, but in this situation, the manufacturing cost of small animal control resin composition becomes too high.In addition, the containing ratio describing the small animal agent for preventing and eliminating made in small animal control resin composition in patent document 2 is the technology of 0.001 % by weight ~ 0.1 % by weight, but in this situation, be difficult to give play to the Repellency effect of suitable small animal and the continuation of this effect.If make the containing ratio of the small animal agent for preventing and eliminating in small animal control resin composition be 1 % by weight ~ 10 % by weight, then can obtain the Repellency effect of small animal and the balance of manufacturing cost.
In the present invention, in the mixture of olefine kind resin (A1), small animal agent for preventing and eliminating (B), slowly-releasing auxiliary agent (C), add polyamide-based resin (A2) and resin material (A3) or add resin material (A4) or add polyamide-based resin (A2), resin material (A3) and resin material (A4), so small animal agent for preventing and eliminating (B) can be improved for the compatibility of olefine kind resin (A1) and slow release, can be made into high-performance and the small animal control resin composition of low cost.
Accompanying drawing explanation
Fig. 1 is the chart of the composition of the small animal control resin composition representing embodiment.
Fig. 2 is the chart of the composition of the small animal control resin composition representing comparative example.
Fig. 3 is the chart of the use material of the small animal control resin composition representing embodiment and comparative example.
Fig. 4 is the chart of the physical property of the small animal control resin composition representing embodiment.
Fig. 5 is the chart of the physical property of the small animal control resin composition representing comparative example.
Embodiment
Below, the formation of the small animal control resin composition involved by embodiment is described.
The small animal control resin composition of this example comprises (A1) olefine kind resin, (B) small animal agent for preventing and eliminating, (C) the slowly-releasing auxiliary agent of small animal agent for preventing and eliminating is as basic composition, in addition, also comprise polyamide-based resin (A2) and (A3) is selected from maleic anhydride modified polyester, maleic anhydride modified polypropylene, at least a kind of resin material of maleic anhydride modified styrene-ethylene-butadiene block copolymer and ethylene-methyl methacrylate glycidyl ester copolymer, or also comprise at least a kind of resin material that (A4) is selected from ethylene-vinyl carboxylate's copolymer and ethene-unsaturated carboxylic acid ester copolymer, or also comprise described polyamide-based resin (A2), be selected from least a kind of described resin material (A3) and be selected from least a kind of resin material (A4).
Olefine kind resin (A1) is the matrix resin for small animal control resin composition being configured as structure, wherein has polyvinyl resin and acrylic resin.As polyvinyl resin, ldpe resin (PE-LD), high-density polyethylene resin (PE-HD), ultra-low density polyethylene resin (PE-VLD), linear low density polyethylene resin (PE-LLD) can be used.In addition, as acrylic resin, homopolymers, ethylene-propylene copolymer and block copolymer can be used.
As small animal agent for preventing and eliminating (B), suitable medicament can be adopted according to the application target of resin combination.Such as, as the medicament preventing and kill off activity with small animals such as various pest, sanitary insect pest and other insects, Araneae, acarid class, mouse, the compound with small animal expellent activity can be illustrated, there is insecticidal activity, acaricidal activity, kill the compound that active spider or activity for rat control etc. kill small animal activity, have ingesting of small animal and hinder active compound, the growth with small animal controls active compound etc.
As the described object lesson with the medicament of small animal control, the chloronicotinyl insecticide of Imidacloprid and so on can be illustrated, the compound formed by the neophyl free radical with silicon atom of silafluofene and so on, Benfuracard micro, alanycarb, metoxadiazone, carbosulfan, Bassa, carbaryl, Methomyl, unden, the carbamate compounds such as fenoxycarb, pyrethrin, allethrin, dl, d-T80-allethrin, d-T80-allethrin, d-T80-resmethrin, bioallethrin, d-T80-tetramethrin, tetramethrin, resmethrin, PH, proparthrin, permethrin, acrinathrin, ether chrysanthemum ester, tralomethrin, phenothrin, d-phenothrin, sumicidin, empenthrin, prallethrin, tefluthrin, the pyrethroid coumpounds such as transfluthrin, dichlorvos, sumithion, basudin, malathion, bromophos, fenthion, chlorophos, 2-dichloroethylk dimethyl phosphate, Swebate, ronnel, chlorpyrifos-methyl, cynock, calvinphos, azamethiphos, pyridaphethione, propetamphos, the organophosphorus compounds such as chlopyrifos, Acetamiprid, Imidacloprid, thiacloprid, Nitenpyram, clothianidin, Diacloden, the anabasine compounds such as MTI-446, and their isomer, derivative, analog etc.In addition, the compound that methoprene, Nylar, kinoprene, hydroprene, sea Nolan, Mount Tai (Japanese: デ オ ヘ ノ ラ Application), NC-170, flufenoxuron, diflubenzuron, lufenuron, chlorine A Zilong (Japanese: Network ロ Le ア ズ ロ Application) etc. have the activity of the growth controlling small animal can be exemplified.In addition, miticide can exemplify dicofol, capillary, tebufenpyrad, pyridaben, milbemectin, fenpyroximate etc., and rodenticide can exemplify red squill, Shoxin, zinc phosphide, thallium sulfate, ANTU, warfarin, endothion, coumarin, coumatetralyl, Bromadiolone, difethialone etc.In addition, following medicament also can be used as the medicament with small animal control of the present invention: the thujaplicin that Taiwan Japan cypress, Thujopsis dolabrata, Japanese Thuja (blue or green gloomy Japan cypress) etc. comprise, the cadinol derivative (α-cadinol, T-cadinol) that vanilla and Japanese cypress comprise, geraniol, firpene, caryophyllene, borneol, eugenol etc. that the sesame oil plants such as cloves, nutmeg, coriander, cumin contain in a large number and reed, China fir etc. have the medicament of the natural origin of the known sesame oil of small animal control etc.
Slowly-releasing auxiliary agent (C) gives olefine kind resin (A1) with the composition of the slow release of small animal agent for preventing and eliminating (B), be better at least a kind of compound being selected from sulfamide derivative, sulfonate derivatives, carboxamide derivative, carboxylic ester derivative, they are considered to have to dissolve and keep small animal agent for preventing and eliminating (B) and the effect of giving slow release.In these slowly-releasing auxiliary agents (C), as carboxylic ester derivative, the Arrcostab, aromatic ester etc. of the various carboxylic acids that can be replaced by hydroxyl, nitro, amino, epoxy radicals, halogen etc. can be illustrated.
As the object lesson of carboxylate, such as repefral can be illustrated, diethyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzyl phthalate, DMEP, 4,5-epoxy hexahydrophthalic acid two (2-Octyl Nitrite), 4,5-epoxy hexahydrophthalic acid two (7,8-epoxy-2-octenylester), 4,5-epoxy hexahydrophthalic acid two (9,10-epoxy stearyl), 4,5-epoxy hexahydrophthalic acid two (10,11-epoxyundecyl base ester), phthalic acid two (tetrahydrofurfuryl oxygen base ethyl ester), the phthalate derivatives such as the ethylene oxide adduct of various phthalic mixed ester and phthalic mixed ester, M-phthalic acid ester derivant, tetrahydrophthalic acid ester derivant, P-hydroxybenzoic acid butoxyethyl, P-hydroxybenzoic acid cyclohexyloxy ethoxy ethoxyethyl acrylate, P-hydroxybenzoic acid-2-Octyl Nitrite, the hydroxybenzoate of ω-alkyl oligoethylene oxide, the benzoate derivatives such as the P-hydroxybenzoic acid addition product of undecyl glycidol ether, the propanoate ester derivatives such as thio-2 acid two (tetrahydrofurfuryl oxygen base ethyl ester), adipate ester derivative, azelate derivative, sebacate derivative, dodecane-2-acid ester derivant, maleate derivative, fumarate derivative, trimellitic acid ester derivant, citric acid three (Butoxyethoxy ethyl ester), citric acid di-n-octyl-mono-(Nonylphenoxy ethyl) ester, citric acid three n-octyl, citric acid dioctyl-(tetrahydrofurfuryl oxygen base ethyl) ester, citric acid three myristyl ester, the citrate ester derivatives such as triethyl citrate, itaconate derivative, the oleate derivatives such as oleic acid tetrahydro furfuryl ester, ricinoleic acid ester derivative, n-butyl lactate, lactic acid-2-Octyl Nitrite, lactic acid n-butoxy ethoxy ethyl ester, lactic acid n-octyloxy ethoxy ethyl ester, the lactic acid ester derivative such as lactic acid n-decyloxy ethoxy ethyl ester, tartaric acid two (octyloxyethoxy ethyl ester), tartaric acid (n-octyl) (Nonylphenoxy ethyl) ester, the tartrate derivatives such as tartaric acid two (octyloxyethoxy ethyl ester), malic acid dibutoxy ethyl ester, malic acid two (n-butoxy ethoxy ethyl ester), malic acid distearyl ester, the malate derivatives such as the different nonyl ester of malic acid octadecylene base, the salicylic acid ester derivatives etc. such as the salicylic acid addition product of benzyl glycidyl ether.In addition, as phosphate derivative, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate (2-Octyl Nitrite), phosphoric acid-2-ethylhexyl-diphenyl, tributoxyethyl phosphate, triphenyl phosphate, phosphoric acid cresyl diphenyl, isodecyl-diphenyl, tricresyl phosphate cresyl ester, tricresyl phosphate (xylyl ester), tricresyl phosphate (chloroethene ester), di(2-ethylhexyl)phosphate tolyl-diphenyl, four (2 can be illustrated, 4-di-tert-butyl-phenyl)-4,4 '-biphenylene bisphosphate etc.
As the object lesson of phosphazene derivative, the cyclic phosphazene compound represented with following general formula (1) can be exemplified; In formula, m represents the integer of 3 ~ 25; R
1, R
2identical or different, the phenyl that represent the alkyl of carbon number 1 ~ 8, can be replaced by the alkyl of carbon number 1 ~ 8 and/or pi-allyl.
In addition, can exemplify the straight-chain phosphazene compound represented with following general formula (2) and at least a kind of phosphazene compound being selected from these phosphazene compounds is adjacent phenylene, metaphenylene, compound to phenylene or biphenylene; In formula, n represents the integer of 3 ~ 1000; R
3, R
4identical or different, the phenyl that represent the alkyl of carbon number 1 ~ 8, can be replaced by the alkyl of carbon number 1 ~ 8 and/or pi-allyl; X represents group-N=P (OR
3)
3, group-N=P (OR
4)
3, group-N=P (O) (OR
3) or group-N=P (O) (OR
4); Y represents group-P (OR
3)
4, group-P (OR
4)
4, group-P (O) (OR
3)
2or group-P (O) (OR
4)
2.
In addition, also can exemplify from substituent R
1, R
2, R
3, R
4slough alkyl etc. and by phosphazene compound that at least a kind of crosslinking group being selected from the group represented with following general formula (3) is crosslinked between 2 oxygen atoms obtaining; In formula, r represent 0 or 1, A represent group-SO
2-,-S-,-O-or-C (CH
3)
2-.
As the object lesson of the cyclic phosphazene compound represented with general formula (1), the cyclic phosphazene compounds such as hexaphenoxycyclotriphosphazene, eight phenoxy group ring four phosphonitriles, ten phenoxy group ring five phosphonitriles, six propoxyl group ring three phosphonitriles, eight propoxyl group ring four phosphonitriles, ten propoxyl group ring five phosphonitriles can be exemplified.
In addition, as the object lesson of the straight-chain phosphazene compound represented with general formula (2), chain phosphazene compound chain two chlorophosphonitrile replacing and has propoxyl group and/or phenoxy group can be exemplified.
As the object lesson of the cross-linked structure represented with general formula (3), such as 4 can be exemplified, 4 '-sulfonyl biphenylene (bis-phenol-S residue), 4,4 '-oxo biphenylene, 4,4 '-sulfo-biphenylene, 4,4 '-biphenylene etc.
These phosphazene derivatives can replace at an arbitrary position amino and/or phenyl amino.These phosphazene derivatives can be used alone a kind in described compound, also can use mixture of more than two kinds.In addition, can be the mixture of cyclic phosphazene and straight-chain phosphonitrile.
In addition, as carboxamide derivative, N-cyclohexylbenzoyl amine etc. can be illustrated.
In addition, as sulfamide derivative, N-methyl benzenesulfonamide, N-ethyl beneznesulfonamide, N-butylbenzenesulfonamide, N-cyclohexyl benzene sulfonamide, N-ethyl para toluene sulfonamide, N-butyl toluene sulfonamide, N-cyclohexyl toluenesulfonamide etc. can be illustrated.
In addition, as sulfonate derivatives, ethyl benzenesulfonat etc. can be illustrated.B component can use be selected from sulfamide derivative, sulfonate derivatives, carboxamide derivative, independent a kind of carboxylic ester derivative, or be selected from the mixture of more than two kinds of these compounds.
Polyamide-based resin (A2) is the carrying resin of carrying small animal agent for preventing and eliminating (B), has the function of the maintenance dose of the small animal agent for preventing and eliminating (B) in adjustment olefine kind resin (A1).As polyamide-based resin (A2), ε-caproamide (PA6), hexamethylene adipamide (PA66), hexamethylene sebacamide (PA610), 11 lactam (PA11), ω-lauramide (PA12), { ε-caproamide/hexamethylene adipamide/hexamethylene sebacamide/ω-lauramide } copolymer can be exemplified.
Resin material (A3) be improve polyamide-based resin (A2) for olefine kind resin (A1) compatibility help dispersion resin, have and make polyamide-based resin (A2) be scattered in function in olefine kind resin (A1) equably.As this resin material (A3), maleic anhydride modified polyethylene (PE-MAH), maleic anhydride modified polypropylene (PP-MAH), maleic anhydride modified styrene-ethylene-butadiene block copolymer (SEBS-MAH), ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA can be exemplified, E-GMA-VA, E-GMA-M).
Resin material (A4) improves the affinity resin of small animal agent for preventing and eliminating (B) for the affinity of olefine kind resin (A1), has the function of adjustment small animal agent for preventing and eliminating (B) from the slowly-releasing amount of olefine kind resin (A1).As this resin material (A4), ethylene-vinyl carboxylate's copolymer or ethene-unsaturated carboxylic acid ester copolymer can be exemplified, more specifically can exemplify vinyl-vinyl acetate copolymer (EVA), ethylene methyl methacrylate copolymer (EMMA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA).
In addition, the inorganic filling material of ormal weight is added with in the small animal control resin composition of embodiment.As inorganic filling material, particle shape inorganic filling material, fibrous inorganic filling material or flakey inorganic filling material can be used.
As particle shape inorganic filling material, can illustrate potassium titanate particle, Titanium particles, monoclinic system Titanium particles, silicon dioxide granule, calcium phosphate particles etc., they can be used alone or as a mixture.In this particle shape inorganic filling material, particularly preferably potassium titanate particle.
As fibrous inorganic filling material, can preferably use such as have 0.05 ~ 10 μm, average fiber footpath, average fiber long 3 ~ 150 μm, be better the fibrous inorganic filling material of shape of 0.1 ~ 7 μm, average fiber footpath, long 5 ~ 50 μm of average fiber, as this fibrous inorganic filling material, can illustrate 4 potassium titanate fibres, 6 potassium titanate fibres, 8 potassium titanate fibres, titanium dioxide fiber, monoclinic system titanium dioxide fiber, silicon dioxide fibre, wollastonite, eakleite etc., they can be used alone or as a mixture.In these fibrous inorganic filling materials, particularly preferably 8 potassium titanate fibres.
As flakey inorganic filling material, can illustrate potassium titanate, potassium titanate lithium, magnesium titanate, talcum, synthetic mica, natural mica, sericite, plate-like aluminum oxide, boron nitride etc., they can be used alone or as a mixture.In this flakey inorganic filling material, particularly preferably potassium titanate.If mix these inorganic filling materials, then slow release can be made to continue for a long time.In addition, inorganic filling material mix the raising being also conducive to mechanical properties.
Also have; inorganic filling material can directly use; also can carry out surface treatment with surface conditioning agents such as silane coupler or titanate coupling agent such as amino silane, epoxy radicals silicone hydride, acryl silane, thus improve the bonding interface with resin, and improve mechanical properties further.
Also have, in the small animal control resin composition of embodiment, it is desirable to make to be more than 1 % by weight or 1 % by weight relative to the containing ratio of the small animal agent for preventing and eliminating (B) of the total amount of small animal control resin composition and less than 10 % by weight or 10 % by weight.If this is because containing ratio is lower than 1 % by weight, then the Repellency effect of small animal reduces, and the continuation of its effect also reduces.On the other hand, if containing ratio is higher than 10 % by weight, then the manufacturing cost of small animal control resin composition raises, and uses olefine kind resin at a low price to be obliterated as the effect of matrix resin.
Small animal control resin composition of the present invention such as carries out melting mixing to manufacture by each composition of fusion.The fusion of each composition has come by carrying out dry type mixing with rotary drum, blender, mixer etc. in advance, also can by the identical or different hopper supply of each composition from mixing roll being carried out.The small animal control resin composition of gained can direct forming be the small animal control resin molded body that required shape is made as goods, also once can extrude rear enforcement and carry out the operations such as granulation by comminutor, and then carry out preserving and circulating.The material that enforcement granulation etc. obtains forms by known method.
When small animal control resin composition is shaped, the known suitable forming processes such as such as injection molded, extrusion molding, extrusion molding, blow molding, shaping by stock removal can be adopted.About the shape of the small animal control resin molded body as goods, be not particularly limited, tabular, bar-shaped, cylindric, pectination, the arbitrary shape such as spherical can be adopted.In addition, except being formed separately by small animal control resin composition, the shaping of two looks or the polychrome combined with metal etc. can also be carried out.
Below, exemplify examples and comparative examples of the present invention, illustrate the effect of small animal control resin composition of the present invention.
Fig. 1 represents the composition of the small animal control resin composition of embodiment 1 ~ 19, and Fig. 2 represents the composition of the small animal control resin composition of comparative example 1 ~ 7.Further, the remaining part of each small animal control resin composition of embodiment 1 ~ 19 and comparative example 1 ~ 7 is inorganic filler, according to illustrated become the subtotaling total amount condition that reaches 100 weight portions adjust, but omit record in these figure.The concrete manufacturer name of use material and trade name are as shown in Figure 3.
Fig. 4 represents the physical property of the small animal control resin composition of embodiment 1 ~ 19, and Fig. 5 represents the physical property of the small animal control resin composition of comparative example 1 ~ 7.About the physical property of small animal control resin composition, the rate of keeping away is avoided to the content of the small animal agent for preventing and eliminating (B) in sample, every 24 hours slowly-releasing amounts from the small animal agent for preventing and eliminating (B) of sample, the amount being present in the small animal agent for preventing and eliminating (B) of specimen surface from being shaped after 24 hours, desinsection quick-acting and insect and evaluates.
The content of the small animal agent for preventing and eliminating (B) in sample passes through liquid chromatography for measuring, using content more than 80% of addition or 80% as appropriate value.
Within every 24 hours, the slowly-releasing amount from the small animal agent for preventing and eliminating (B) of sample is by liquid chromatography for measuring, by 5 μ g/cm
224 hours or 5 μ g/cm
2the content of more than 24 hours is as appropriate value.
For the total amount comprising the liquid component of small animal agent for preventing and eliminating (B) and slowly-releasing auxiliary agent being present in specimen surface after 24 hours from being shaped, with the surface of alcohol flushing sample, measure the weight difference before and after it, by 100 μ g/cm
2or 100 μ g/cm
2following as appropriate value.
For desinsection quick-acting, use 10 Groton bugs, tested by continuous contact method, using within 10 minutes as appropriate value.
The evaluation that insect avoids the rate of keeping away is undertaken by sanctuary's test.Specifically, in the acrylic resin container with the end (vertical 300mm, horizontal 230mm, high 250mm) that top is open, 2 sanctuarys of place (vertical 60mm, horizontal 60mm, high 10mm) A, B of bait and water being set and can hiding for insect.Sanctuary A is provided with the described sample formed by small animal control resin composition in inside, sanctuary B does not arrange described sample in inside.10 Groton bugs are put into described acrylic resin container, let alone freely after movable 10 hours, sanctuary A, B is taken out from described acrylic resin container, count the quantity of the Groton bug in each sanctuary, calculate and avoid by avoiding the rate of keeping away [the %]=formula of { borer population of (borer population of the borer population-sanctuary A of sanctuary B)/sanctuary B } × 100 rate of keeping away.The insect evaluation of avoiding the rate of keeping away using more than 90% or 90% as appropriate value.
As shown in Figure 4, the small animal control resin composition of embodiment 1 ~ 19, small animal agent for preventing and eliminating (B) all containing more than 0.9 % by weight or 0.9 % by weight in sample, from the slowly-releasing amount of the small animal agent for preventing and eliminating (B) of sample more than 5 μ g/cm
224 hours, the amount being present in the small animal agent for preventing and eliminating (B) of specimen surface from being shaped after 24 hours was 100 μ g/cm
2or 100 μ g/cm
2below, desinsection quick-acting is within 10 minutes, and it is more than 90% or 90% that insect avoids the rate of keeping away.
On the other hand, as shown in Figure 5, the small animal control resin composition of comparative example 1,2,4,6,7, does not all reach 5 μ g/cm from the slowly-releasing amount of the small animal agent for preventing and eliminating (B) of sample
224 hours, the amount being present in the small animal agent for preventing and eliminating (B) of specimen surface from being shaped after 24 hours was more than 100 μ g/cm
2.In addition, for the small animal control resin composition of comparative example 3,5, natively cannot keep the shape specified, be not suitable as goods.
From the above results, the small animal control resin composition of embodiment 1 ~ 19 can improve small animal agent for preventing and eliminating (B) for the compatibility of olefine kind resin (A1) and slow release, can make high-performance and the small animal control resin composition of low cost.
The possibility that industry utilizes
The present invention can be used for the small animal control resin molded body preventing and kill off the small animals such as various pest, sanitary insect pest and other insects, Araneae, acarid class, mouse.
Claims (3)
1. a small animal control resin composition, it is characterized in that, comprise: the olefine kind resin (A1) small animal control resin composition being configured as the matrix resin of structure, small animal agent for preventing and eliminating (B), give olefine kind resin (A1) with the slowly-releasing auxiliary agent (C) of the slow release of small animal agent for preventing and eliminating (B), the polyamide-based resin (A2) of carrying small animal agent for preventing and eliminating (B), and improve polyamide-based resin (A2) for olefine kind resin (A1) compatibility be selected from maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, at least a kind of resin material (A3) of maleic anhydride modified styrene-ethylene-butadiene block copolymer and ethylene-methyl methacrylate glycidyl ester copolymer,
The total amount comprising the liquid component of small animal agent for preventing and eliminating (B) and slowly-releasing auxiliary agent (C) being present in formed products surface from being shaped after 24 hours is 100 μ g/cm
2below, afterwards every 24 hours small animal agent for preventing and eliminating (B) slowly-releasing amount be 5 μ g/cm
2more than 24 hours.
2. a small animal control resin composition, it is characterized in that, comprise: the olefine kind resin (A1) small animal control resin composition being configured as the matrix resin of structure, small animal agent for preventing and eliminating (B), give olefine kind resin (A1) with the slowly-releasing auxiliary agent (C) of the slow release of small animal agent for preventing and eliminating (B), the polyamide-based resin (A2) of carrying small animal agent for preventing and eliminating (B), improve polyamide-based resin (A2) for olefine kind resin (A1) compatibility be selected from maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, at least a kind of resin material (A3) of maleic anhydride modified styrene-ethylene-butadiene block copolymer and ethylene-methyl methacrylate glycidyl ester copolymer, and improve at least a kind resin material (A4) that be selected from ethylene-vinyl carboxylate copolymer and ethene-unsaturated carboxylic acid ester copolymer of small animal agent for preventing and eliminating (B) for the affinity of olefine kind resin (A1),
The total amount comprising the liquid component of small animal agent for preventing and eliminating (B) and slowly-releasing auxiliary agent (C) being present in formed products surface from being shaped after 24 hours is 100 μ g/cm
2below, afterwards every 24 hours small animal agent for preventing and eliminating (B) slowly-releasing amount be 5 μ g/cm
2more than 24 hours.
3. small animal control resin composition as claimed in claim 1 or 2, it is characterized in that, make the containing ratio of (B) small animal agent for preventing and eliminating of the total amount relative to described small animal control resin composition be more than 1 % by weight or 1 % by weight and less than 10 % by weight or 10 % by weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-143863 | 2010-06-24 | ||
| JP2010143863A JP5604753B2 (en) | 2010-06-24 | 2010-06-24 | Small animal control resin composition |
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| CN102334474B true CN102334474B (en) | 2015-01-21 |
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| CN104411168A (en) * | 2012-07-13 | 2015-03-11 | 日本环境化学株式会社 | Anti-bioactive particles and method for manufacturing same |
| JP2015013813A (en) * | 2013-07-03 | 2015-01-22 | フクビ化学工業株式会社 | Agent-containing resin molded form |
| JP2015078141A (en) * | 2013-10-15 | 2015-04-23 | 株式会社ニックス | Controlled release resin composition |
| JP2015078138A (en) * | 2013-10-15 | 2015-04-23 | 株式会社ニックス | Small animal pest control resin composition |
| CN103756101A (en) * | 2014-01-23 | 2014-04-30 | 上海宇泽贸易有限公司 | Polymer composite material with organism killing function and preparation process |
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| CN1587452A (en) * | 2004-08-12 | 2005-03-02 | 上海公泰纺织制品有限公司 | Process for producing insect-proof polyolefine fiber |
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| JPH09169916A (en) * | 1995-12-19 | 1997-06-30 | Fukuvi Chem Ind Co Ltd | Insectproof resin composition and molded form thereof |
| JPH10167907A (en) * | 1996-12-05 | 1998-06-23 | Daiwa Kagaku Kogyo Kk | Molding product for pest control |
| JP4361152B2 (en) * | 1999-01-18 | 2009-11-11 | 大塚化学株式会社 | Small animal control resin composition and small animal control member formed by molding the resin composition |
| JP2000319105A (en) * | 1999-05-12 | 2000-11-21 | Sumika Raifuteku Kk | Resin preparation for controlling insect pest |
| JP4448595B2 (en) * | 2000-03-31 | 2010-04-14 | 住友化学株式会社 | Resin composition and molded body |
| JP2002047110A (en) * | 2000-08-01 | 2002-02-12 | Sumitomo Chem Co Ltd | Insect-proof resin composition and insect-proof molded article |
| JP5117073B2 (en) * | 2007-02-28 | 2013-01-09 | 住友化学株式会社 | Ant-proof sheet |
| JP2010013614A (en) * | 2008-07-03 | 2010-01-21 | Nix Inc | Insect-proof/repelling resin molded form |
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| CN1993044A (en) * | 2004-08-06 | 2007-07-04 | 日本曹达株式会社 | Agricultural-chemical preparation having controlled releasability |
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|---|---|
| JP5604753B2 (en) | 2014-10-15 |
| CN102334474A (en) | 2012-02-01 |
| JP2012006868A (en) | 2012-01-12 |
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