JP2016108299A - Agricultural chemical active ingredient release control agent and gradually releasable agricultural chemical composition - Google Patents
Agricultural chemical active ingredient release control agent and gradually releasable agricultural chemical composition Download PDFInfo
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- JP2016108299A JP2016108299A JP2014249536A JP2014249536A JP2016108299A JP 2016108299 A JP2016108299 A JP 2016108299A JP 2014249536 A JP2014249536 A JP 2014249536A JP 2014249536 A JP2014249536 A JP 2014249536A JP 2016108299 A JP2016108299 A JP 2016108299A
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- 239000003905 agrochemical Substances 0.000 title claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 34
- 239000004480 active ingredient Substances 0.000 title claims abstract description 32
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- 125000003118 aryl group Chemical group 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000012868 active agrochemical ingredient Substances 0.000 claims description 16
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- 239000005586 Nicosulfuron Substances 0.000 description 1
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- 239000005950 Oxamyl Substances 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- 229930006000 Sucrose Natural products 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- OIPMQULDKWSNGX-UHFFFAOYSA-N bis[[ethoxy(oxo)phosphaniumyl]oxy]alumanyloxy-ethoxy-oxophosphanium Chemical compound [Al+3].CCO[P+]([O-])=O.CCO[P+]([O-])=O.CCO[P+]([O-])=O OIPMQULDKWSNGX-UHFFFAOYSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
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- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- QAYICIQNSGETAS-UHFFFAOYSA-N dazomet Chemical compound CN1CSC(=S)N(C)C1 QAYICIQNSGETAS-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- CSNCOKSAYUDNIE-UHFFFAOYSA-N diethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OCC)C=CC2=CC(C(=O)OCC)=CC=C21 CSNCOKSAYUDNIE-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- GGCUUOGRTPMFQK-UHFFFAOYSA-N dimethyl cyclohexane-1,1-dicarboxylate Chemical compound COC(=O)C1(C(=O)OC)CCCCC1 GGCUUOGRTPMFQK-UHFFFAOYSA-N 0.000 description 1
- OCSXMIBZIHMVCP-UHFFFAOYSA-N dimethyl naphthalene-1,4-dicarboxylate Chemical compound C1=CC=C2C(C(=O)OC)=CC=C(C(=O)OC)C2=C1 OCSXMIBZIHMVCP-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- SYJFEGQWDCRVNX-UHFFFAOYSA-N diquat Chemical compound C1=CC=[N+]2CC[N+]3=CC=CC=C3C2=C1 SYJFEGQWDCRVNX-UHFFFAOYSA-N 0.000 description 1
- LNTZHXQMPUKVNX-UHFFFAOYSA-N docosyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOP(O)(O)=O LNTZHXQMPUKVNX-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- KGVPNLBXJKTABS-UHFFFAOYSA-N hymexazol Chemical compound CC1=CC(O)=NO1 KGVPNLBXJKTABS-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CGTYPNOFVGYUED-UHFFFAOYSA-N methyl 2-(2-methoxycarbonylphenyl)benzoate Chemical compound COC(=O)C1=CC=CC=C1C1=CC=CC=C1C(=O)OC CGTYPNOFVGYUED-UHFFFAOYSA-N 0.000 description 1
- ZQEIXNIJLIKNTD-UHFFFAOYSA-N methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alaninate Chemical compound COCC(=O)N(C(C)C(=O)OC)C1=C(C)C=CC=C1C ZQEIXNIJLIKNTD-UHFFFAOYSA-N 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RTCOGUMHFFWOJV-UHFFFAOYSA-N nicosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(=O)N(C)C)=N1 RTCOGUMHFFWOJV-UHFFFAOYSA-N 0.000 description 1
- KZAUOCCYDRDERY-UHFFFAOYSA-N oxamyl Chemical compound CNC(=O)ON=C(SC)C(=O)N(C)C KZAUOCCYDRDERY-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JHNMPYMTHAMTJM-UHFFFAOYSA-N phenyl-(2,3,4,5-tetramethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC(C(=O)C=2C=CC=CC=2)=C1C JHNMPYMTHAMTJM-UHFFFAOYSA-N 0.000 description 1
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- DNVLJEWNNDHELH-UHFFFAOYSA-N thiocyclam Chemical compound CN(C)C1CSSSC1 DNVLJEWNNDHELH-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
本発明は、農薬活性成分の溶出速度を抑制し、薬効を長期に持続させ、農作物に対する薬害を低減する農薬活性成分放出制御剤及び徐放性農薬組成物に関する。 The present invention relates to a pesticidal active ingredient release control agent and sustained release pesticidal composition that suppresses the dissolution rate of pesticidal active ingredients, maintains the efficacy for a long period of time, and reduces phytotoxicity to agricultural crops.
従来、農薬活性成分放出制御剤や徐放性農薬組成物として、農薬活性成分に加えてパラフィンワックスや粘度鉱物や界面活性剤等を含有するもの（例えば、特許文献１参照）、農薬活性成分を含む農薬粒剤を熱硬化性樹脂を主成分とする樹脂被膜で被覆するもの（例えば、特許文献２参照）、農薬活性成分をポリ乳酸樹脂で被覆するもの（例えば、特許文献３参照）、粒剤製造時にポリ乳酸樹脂をエマルション化したものを練り合わせるもの（例えば、特許文献４参照）等が提案されている。しかし、これら従来の農薬用活性成分放出制御剤や徐放性農薬組成物には、農薬活性成分の放出制御効果が不十分という問題がある。 Conventionally, as an agrochemical active ingredient release control agent or sustained-release agrochemical composition, in addition to the agrochemical active ingredient, those containing paraffin wax, viscous minerals, surfactants, etc. (see, for example, Patent Document 1), A coating containing a pesticide granule containing a resin film containing a thermosetting resin as a main component (for example, see Patent Document 2), a pesticide active ingredient coated with a polylactic acid resin (for example, see Patent Document 3), a grain There have been proposed ones in which an emulsion of a polylactic acid resin is kneaded (for example, see Patent Document 4). However, these conventional active ingredient release control agents for agricultural chemicals and sustained release agricultural chemical compositions have a problem that the effect of controlling the release of the agricultural chemical active ingredient is insufficient.
本発明が解決しようとする課題は、農薬活性成分が水溶解度の高いものであっても優れた放出制御効果を示す農薬活性成分放出制御剤及びかかる農薬活性成分放出制御剤を含有する徐放性農薬組成物を提供する処にある。 The problem to be solved by the present invention is that a pesticidal active ingredient release controlling agent exhibiting an excellent release controlling effect even if the pesticidal active ingredient has a high water solubility, and sustained release containing such a pesticide active ingredient releasing controlling agent It is in place to provide an agrochemical composition.
本発明者らは、前記の課題を解決するべく研究した結果、特定の五つの構成単位が特定の割合から構成された特定の数平均分子量のポリエステル樹脂を含有して成る農薬活性成分放出制御剤が正しく好適であることを見出した。 As a result of researches to solve the above-mentioned problems, the present inventors have determined that an agricultural chemical active ingredient release control agent comprising a polyester resin having a specific number average molecular weight in which specific five constituent units are composed of a specific ratio. Has been found to be correct and suitable.
すなわち本発明は、下記の構成単位Ａが９〜４８．５モル％、下記の構成単位Ｂが０．５〜３０モル％、下記の構成単位Ｃが５〜４８モル％、下記の構成単位Ｄが２〜４５モル％及び下記の構成単位Ｅが１〜４０モル％（合計１００モル％）の割合から構成され、数平均分子量が５０００〜１０００００であるポリエステル樹脂を含有して成ることを特徴とする農薬活性成分放出制御剤に係る。また本発明は、かかる農薬活性成分放出制御剤を含有する徐放性農薬組成物に係る。 That is, the present invention includes the following structural unit A of 9 to 48.5 mol%, the following structural unit B of 0.5 to 30 mol%, the following structural unit C of 5 to 48 mol%, and the following structural unit D. Characterized in that it comprises a polyester resin having a number average molecular weight of 5,000 to 100,000, comprising 2 to 45 mol% and the following structural unit E having a ratio of 1 to 40 mol% (total 100 mol%). The present invention relates to an agrochemical active ingredient release control agent. The present invention also relates to a sustained-release agrochemical composition containing such an agrochemical active ingredient release control agent.
構成単位Ａ：炭素数８〜１２の芳香族ジカルボン酸から形成された構成単位及び／又は炭素数８〜１２の芳香族ジカルボン酸のエステル形成性誘導体から形成された構成単位 Structural unit A: a structural unit formed from an aromatic dicarboxylic acid having 8 to 12 carbon atoms and / or a structural unit formed from an ester-forming derivative of an aromatic dicarboxylic acid having 8 to 12 carbon atoms
構成単位Ｂ：分子中にスルホン酸塩基を有する炭素数８〜１２の芳香族ジカルボン酸の塩から形成された構成単位、分子中にスルホン酸塩基を有する炭素数８〜１２の芳香族ジカルボン酸のエステル形成性誘導体の塩から形成された構成単位、炭素数９〜２０の３又は４価の芳香族ポリカルボン酸から形成された構成単位及び炭素数９〜２０の３又は４価の芳香族ポリカルボン酸のエステル形成性誘導体から形成された構成単位から選ばれる一つ又は二つ以上 Structural unit B: a structural unit formed from a salt of an aromatic dicarboxylic acid having 8 to 12 carbon atoms having a sulfonate group in the molecule, an aromatic dicarboxylic acid having 8 to 12 carbon atoms having a sulfonate group in the molecule A structural unit formed from a salt of an ester-forming derivative, a structural unit formed from a tri- or tetravalent aromatic polycarboxylic acid having 9 to 20 carbon atoms, and a tri- or tetravalent aromatic poly having 9 to 20 carbon atoms One or more selected from structural units formed from ester-forming derivatives of carboxylic acids
構成単位Ｃ：エチレングリコールから形成された構成単位及び／又はプロピレングリコールから形成された構成単位 Structural unit C: a structural unit formed from ethylene glycol and / or a structural unit formed from propylene glycol
構成単位Ｄ：炭素数４〜１０のジオールから形成された構成単位及び／又は分子中に炭素数２〜４のオキシアルキレン単位で構成されたポリオキシアルキレン基を有する分子量４００〜５０００のポリアルキレングリコールから形成された構成単位 Structural unit D: a structural unit formed from a diol having 4 to 10 carbon atoms and / or a polyalkylene glycol having a molecular weight of 400 to 5000 having a polyoxyalkylene group composed of an oxyalkylene unit having 2 to 4 carbon atoms in the molecule Unit formed from
構成単位Ｅ：炭素数４〜２２の脂肪族ジカルボン酸から形成された構成単位及び／又は炭素数４〜２２の脂肪族ジカルボン酸のエステル形成性誘導体から形成された構成単位 Structural unit E: a structural unit formed from an aliphatic dicarboxylic acid having 4 to 22 carbon atoms and / or a structural unit formed from an ester-forming derivative of an aliphatic dicarboxylic acid having 4 to 22 carbon atoms
先ず、本発明に係る農薬活性成分放出制御剤（以下、本発明の放出制御剤という）について説明する。本発明の放出制御剤は、前記の構成単位Ａが９〜４８．５モル％、前記の構成単位Ｂが０．５〜３０モル％、前記の構成単位Ｃが５〜４８モル％、前記の構成単位Ｄが２〜４５モル％及び前記の構成単位Ｅが１〜４０モル％（合計１００モル％）の割合から構成され、数平均分子量が５０００〜１０００００であるポリエステル樹脂を含有して成るものである。ポリエステル樹脂中の構成単位の割合は、ＮＭＲ法により求められ、ポリエステル樹脂を重クロロホルムへ溶解させ、１ＨＮＭＲ測定から得られるピーク面積から算出できる。また数平均分子量はＧＰＣ法により求められ、分子量は標準ポリスチレンより作成した検量線を用いて算出できる。 First, the agricultural chemical active ingredient release control agent (hereinafter referred to as the release control agent of the present invention) according to the present invention will be described. In the release controlling agent of the present invention, the structural unit A is 9 to 48.5 mol%, the structural unit B is 0.5 to 30 mol%, the structural unit C is 5 to 48 mol%, Containing a polyester resin having a constitutional unit D of 2 to 45 mol% and a constitutional unit E of 1 to 40 mol% (total of 100 mol%) and having a number average molecular weight of 5,000 to 100,000 It is. The proportion of the structural unit in the polyester resin is determined by NMR method, and can be calculated from the peak area obtained from 1 HNMR measurement by dissolving the polyester resin in deuterated chloroform. The number average molecular weight is determined by the GPC method, and the molecular weight can be calculated using a calibration curve prepared from standard polystyrene.
構成単位Ａとしては、１）フタル酸、イソフタル酸、テレフタル酸、２，６−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸、１，４−ナフタレンジカルボン酸等の、炭素数８〜１２の芳香族ジカルボン酸から形成された構成単位、２）フタル酸ジメチル、イソフタル酸ジメチル、テレフタル酸ジメチル、２，６−ナフタレンジカルボン酸ジメチル、２，６−ナフタレンジカルボン酸ジエチル、１，４−ナフタレンジカルボン酸ジメチル等の、炭素数８〜１２の芳香族ジカルボン酸のエステル形成性誘導体から形成された構成単位が挙げられる。 As the structural unit A, 1) aroma having 8 to 12 carbon atoms such as phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, etc. Units formed from aromatic dicarboxylic acids, 2) dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, diethyl 2,6-naphthalenedicarboxylate, dimethyl 1,4-naphthalenedicarboxylate And a structural unit formed from an ester-forming derivative of an aromatic dicarboxylic acid having 8 to 12 carbon atoms.
構成単位Ｂとしては、１）スルホフタル酸のアルカリ金属塩、スルホイソフタル酸のアルカリ金属塩、スルホテレフタル酸のアルカリ金属塩、スルホフタル酸のアルカリ土類金属塩、スルホイソフタル酸のアルカリ土類金属塩、スルホテレフタル酸のアルカリ土類金属塩、スルホ＝２，６−ナフタレンジカルボン酸のアルカリ金属塩、スルホ＝２，３−ナフタレンジカルボン酸のアルカリ金属塩、スルホ＝１，４−ナフタレンジカルボン酸のアルカリ金属塩、スルホ＝２，６−ナフタレンジカルボン酸のアルカリ土類金属塩、スルホ＝２，３−ナフタレンジカルボン酸のアルカリ土類金属塩、スルホ＝１，４−ナフタレンジカルボン酸のアルカリ土類金属塩等の、分子中にスルホン酸塩基を有する炭素数８〜１２の芳香族ジカルボン酸の塩から形成された構成単位、２）スルホフタル酸ジメチルのアルカリ金属塩、スルホイソフタル酸ジメチルのアルカリ金属塩、スルホテレフタル酸ジメチルのアルカリ金属塩、スルホフタル酸ジメチルのアルカリ土類金属塩、スルホイソフタル酸ジメチルのアルカリ土類金属塩、スルホテレフタル酸ジメチルのアルカリ土類金属塩、スルホ＝２，６−ナフタレンジカルボン酸ジメチルのアルカリ金属塩、スルホ＝２，３−ナフタレンジカルボン酸ジメチルのアルカリ金属塩、スルホ＝１，４−ナフタレンジカルボン酸ジメチルのアルカリ金属塩、スルホ＝２，６−ナフタレンジカルボン酸ジメチルのアルカリ土類金属塩、スルホ＝２，３−ナフタレンジカルボン酸ジメチルのアルカリ土類金属塩、スルホ＝１，４−ナフタレンジカルボン酸ジメチルのアルカリ土類金属塩等の、分子中にスルホン酸塩基を有する炭素数８〜１２の芳香族ジカルボン酸のエステル形成性誘導体の塩から形成された構成単位、３）トリメリット酸、ピロメリット酸、トリメシン酸、ベンゾフェノンテトラカルボン酸、ビフェニル−２，２’−ジカルボン酸、無水トリメリット酸、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸等の、炭素数９〜２０の３又は４価の芳香族ポリカルボン酸から形成された構成単位、４）トリメリット酸トリメチル、ピロメリット酸テトラメチル、トリメシン酸トリメチル、ベンゾフェノンテトラカルボン酸テトラメチル、ビフェニル−２，２’−ジカルボン酸ジメチル等の、炭素数９〜２０の３又は４価の芳香族ポリカルボン酸のエステル形成性誘導体から形成された構成単位が挙げられる。 As the structural unit B, 1) an alkali metal salt of sulfophthalic acid, an alkali metal salt of sulfoisophthalic acid, an alkali metal salt of sulfoterephthalic acid, an alkaline earth metal salt of sulfophthalic acid, an alkaline earth metal salt of sulfoisophthalic acid, Sulfoterephthalic acid alkaline earth metal salt, sulfo = 2,6-naphthalenedicarboxylic acid alkali metal salt, sulfo = 2,3-naphthalenedicarboxylic acid alkali metal salt, sulfo = 1,4-naphthalenedicarboxylic acid alkali metal Salts, alkaline earth metal salts of sulfo = 2,6-naphthalenedicarboxylic acid, alkaline earth metal salts of sulfo = 2,3-naphthalenedicarboxylic acid, alkaline earth metal salts of sulfo = 1,4-naphthalenedicarboxylic acid, etc. Or a salt of an aromatic dicarboxylic acid having 8 to 12 carbon atoms and having a sulfonate group in the molecule 2) Alkali metal salt of dimethyl sulfophthalate, Alkali metal salt of dimethyl sulfoisophthalate, Alkali metal salt of dimethyl sulfoterephthalate, Alkaline earth metal salt of dimethyl sulfophthalate, Alkali of dimethyl sulfoisophthalate Earth metal salt, alkali earth metal salt of dimethyl sulfoterephthalate, alkali metal salt of sulfo dimethyl 2,6-naphthalenedicarboxylate, alkali metal salt of sulfo dimethyl 2,3-naphthalenedicarboxylate, sulfo = 1, Alkaline metal salt of dimethyl 4-naphthalenedicarboxylate, alkaline earth metal salt of sulfo = 2,6-naphthalenedicarboxylic acid dimethyl, alkaline earth metal salt of sulfo = 2,3-naphthalenedicarboxylic acid, sulfo = 1,4 -Dimethyl naphthalenedicarboxylic acid A structural unit formed from a salt of an ester-forming derivative of an aromatic dicarboxylic acid having 8 to 12 carbon atoms having a sulfonate group in the molecule, such as an alkaline earth metal salt of 3), 3) trimellitic acid, pyromellitic acid , Trimesic acid, benzophenone tetracarboxylic acid, biphenyl-2,2′-dicarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, etc., trivalent or tetravalent aromatic having 9 to 20 carbon atoms Structural units formed from polycarboxylic acids, 4) 9 carbon atoms such as trimethyl trimellitic acid, tetramethyl pyromellitic acid, trimethyl trimesic acid, tetramethyl benzophenone tetracarboxylic acid, dimethyl biphenyl-2,2'-dicarboxylate Formed from ester-forming derivatives of -20 tri- or tetravalent aromatic polycarboxylic acids Structural units.
構成単位Ｃとしては、エチレングリコール、プロピレングリコールから形成された構成単位が挙げられる。 Examples of the structural unit C include structural units formed from ethylene glycol and propylene glycol.
構成単位Ｄとしては、１）１，３−プロパンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、１，８−オクタンジオール、１，１０−デカンジオール等の、炭素数４〜１０のジオールから形成された構成単位、２）分子中にオキシエチレン、オキシプロピレン、オキシブチレン等の炭素数２〜４のオキシアルキレン単位で構成されたポリオキシアルキレン基を有する分子量４００〜５０００のポリアルキレングリコールから形成された構成単位が挙げられる。 As the structural unit D, 1) carbon such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, etc. Structural units formed from diols of several 4 to 10 2) Molecular weight having a polyoxyalkylene group composed of oxyalkylene units of 2 to 4 carbon atoms such as oxyethylene, oxypropylene and oxybutylene in the molecule 400 to 400 Examples include structural units formed from 5000 polyalkylene glycols.
構成単位Ｅとしては、１）コハク酸、アジピン酸、スベリン酸、アゼライン酸、セバシン酸、α、ω−ドデカンジカルボン酸、ドデシルコハク酸、オクタデカンジカルボン酸、シクロヘキサンジカルボン酸等の、炭素数４〜２２の脂肪族ジカルボン酸から形成された構成単位、２）コハク酸ジメチル、アジピン酸ジメチル、スベリン酸ジメチル、アゼライン酸ジメチル、セバシン酸ジメチル、α、ω−ドデカンジカルボン酸ジメチル、ドデシルコハク酸ジメチル、オクタデカンジカルボン酸ジメチル、シクロヘキサンジカルボン酸ジメチル等の、炭素数４〜２２の脂肪族ジカルボン酸のエステル形成性誘導体から形成された構成単位が挙げられる As the structural unit E, 1) C 4-22 such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, α, ω-dodecanedicarboxylic acid, dodecylsuccinic acid, octadecanedicarboxylic acid, cyclohexanedicarboxylic acid, etc. 2) Dimethyl succinate, dimethyl adipate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, α, ω-dimethyl dodecane dicarboxylate, dimethyl dodecyl succinate, octadecanedicarboxylic acid And structural units formed from ester-forming derivatives of aliphatic dicarboxylic acids having 4 to 22 carbon atoms, such as dimethyl acid and dimethyl cyclohexanedicarboxylate.
本発明の放出制御剤としては、前記したポリエステル樹脂以外に、更に下記の樹脂、下記のワックス、有機リン酸エステル及び有機リン酸エステルの塩から選ばれる一つ又は二つ以上を含有して成るものが好ましい。 The release control agent of the present invention contains, in addition to the above-described polyester resin, one or more selected from the following resins, the following waxes, organic phosphate esters, and salts of organic phosphate esters. Those are preferred.
樹脂：ポリ酢酸ビニル、酢酸ビニル-エチレン共重合物、ポリウレタン及びポリオレフィンから選ばれる一つ又は二つ以上 Resin: One or more selected from polyvinyl acetate, vinyl acetate-ethylene copolymer, polyurethane and polyolefin
ワックス：カルナバワックス、パラフィンワックス、ヒマシ硬化油、菜種硬化油及びパーム硬化油から選ばれる一つ又は二つ以上 Wax: one or more selected from carnauba wax, paraffin wax, castor oil, rapeseed oil and palm oil
前記の有機リン酸エステルとしては、分子中に、１）ミリスチル基、セチル基、ステアリル基、エイコシル基、ベヘニル基、テトラコシル基、イソステアリル基等の炭素数１４〜２４の飽和脂肪族炭化水素基、２）ミリストオレイル基、オレイル基、エイコセニル基、テトラコセニル基等の炭素数１４〜２４の不飽和脂肪族炭化水素基を有するものが挙げられるが、なかでも分子中にステアリル基、ベヘニル基、エイコシル基、オレイル基等の炭素数１８〜２２の脂肪族炭化水素基を有する有機リン酸エステルが好ましい。 Examples of the organic phosphate ester include 1) a saturated aliphatic hydrocarbon group having 14 to 24 carbon atoms such as 1) myristyl group, cetyl group, stearyl group, eicosyl group, behenyl group, tetracosyl group, and isostearyl group. 2) Those having an unsaturated aliphatic hydrocarbon group having 14 to 24 carbon atoms such as a myristooleyl group, an oleyl group, an eicosenyl group, a tetracocenyl group, etc., among which a stearyl group, a behenyl group, Organophosphates having an aliphatic hydrocarbon group having 18 to 22 carbon atoms such as an eicosyl group and an oleyl group are preferred.
また前記の有機リン酸エステルの塩としては、前記した有機リン酸エステルとのアルカリ金属塩、有機アンモニウム塩、アンモニウム塩が挙げられる。具体的には、前記した有機リン酸エステルのカリウム塩、ナトリウム塩、リチウム塩等のアルカリ金属塩、トリエタノールアンモニウム塩、ジエタノールアンモニウム塩、モノエタノールアンモニウム塩、トリメチルアンモニウム塩、トリエチルアンモニウム塩、トリブチルアンモニウム塩等の有機アンモニウム塩、更にはアンモニウム塩等が挙げられ、なかでもカリウム塩、ナトリウム塩、ジエタノールアンモニウム塩、トリエタノールアンモニウム塩が好ましい。 Examples of the salt of the organic phosphate include alkali metal salts, organic ammonium salts, and ammonium salts with the above-described organic phosphates. Specifically, alkali metal salts such as potassium salts, sodium salts, and lithium salts of the above-described organophosphates, triethanolammonium salt, diethanolammonium salt, monoethanolammonium salt, trimethylammonium salt, triethylammonium salt, tributylammonium Examples include organic ammonium salts such as salts, and ammonium salts. Among them, potassium salts, sodium salts, diethanolammonium salts, and triethanolammonium salts are preferable.
本発明の放出制御剤は、その組成比率に特に制限はないが、ポリエステル樹脂を２０〜８０質量％、樹脂、ワックス、有機リン酸エステル及び有機リン酸エステルの塩から選ばれる一つ又は二つ以上を合計で２０〜８０質量％（全合計１００質量％）の割合で含有して成るものが好ましい。 The composition of the release control agent of the present invention is not particularly limited, but one or two selected from 20 to 80% by mass of a polyester resin, a resin, a wax, an organic phosphate, and a salt of an organic phosphate. What comprises the above in the ratio of 20-80 mass% in total (total 100 mass% in total) is preferable.
次に、本発明に係る徐放性農薬組成物（以下、本発明の農薬組成物という）について説明する。本発明の農薬組成物は、本発明の放出制御剤、農薬活性成分及び増量剤を含有してなるものである。その組成比率に特に制限はないが、本発明の放出制御剤１００質量部に対し、農薬活性成分１〜５００質量部及び増量剤２００〜２０００質量部を含有して成るものが好ましい。 Next, the sustained release agricultural chemical composition according to the present invention (hereinafter referred to as the agricultural chemical composition of the present invention) will be described. The agrochemical composition of the present invention comprises the release control agent, the agrochemical active ingredient and the bulking agent of the present invention. Although there is no restriction | limiting in particular in the composition ratio, What contains 1-500 mass parts of pesticidal active ingredients and 200-2000 mass parts of extenders with respect to 100 mass parts of release control agents of this invention is preferable.
本発明の農薬組成物に供する農薬活性成分としては、２０℃における水溶解度が０．００５〜８０ｇ／１００mlである農薬活性成分であり、その具体例としてピメトロジン（水溶解度＝０．０３）、カルボフラン（水溶解度＝０．０３）、メソミル（水溶解度＝５．７９）、エチオフェンカルブ（水溶解度＝０．１８）、アセフェート（水溶解度＝７９．０）、ジメトエート（水溶解度＝２．５）、チオシクラム（水溶解度＝８．０ｇ）、ピリミカーブ（水溶解度＝０．３）、オキサミル（水溶解度＝２８．０）等の殺虫剤、シモキサニル（水溶解度＝０．１）、ヒドロキシイソキサゾール（水溶解度＝８．５）、メタラキシル（水溶解度＝０．７１）、ホセチルアルミ（水溶解度＝１２．０）、イミノクタジン酢酸塩（水溶解度＝７６．４）、ダゾメット（水溶解度＝０．３）、ジメチリモール（水溶解度＝０．１２）、ピロキロン（水溶解度＝０．４）等の殺菌剤、アロキシジム（水溶解度＞２００）、ジメタクロール（水溶解度＝０．２）、セトキシジム（水溶解度＝０．４７）、ニコスルフロン（水溶解度＝０．００７）、ジクワット（水溶解度＝７０）等の除草剤、ジクロルプロップ（水溶解度＝０．０３５）、ダミノジット（水溶解度＝１０）等の植物成長調節剤等が挙げられる。農薬活性成分としては、以上例示したような農薬活性成分から選ばれる一つ又は二つ以上を使用できる。また本発明の農薬組成物に供する増量剤としては、１）ベントナイト、タルク、クレー、珪藻土、無晶形二酸化ケイ素、炭酸カルシウム、炭酸マグネシウム等の無機質微粉体、２）硫酸ナトリウム、硫酸アンモニウム、塩化カリウム、尿素等の低分子水溶性化合物、３）グルコース、果糖、蔗糖、乳糖等の糖類、４）微結晶セルロース、木粉、米糠、ふすま、モミガラ等の有機質粉末等が挙げられ、なかでも無機質微粉体が好ましい。 The pesticidal active ingredient used in the pesticidal composition of the present invention is an agrochemical active ingredient having a water solubility of 0.005 to 80 g / 100 ml at 20 ° C., and specific examples thereof include pymetrozine (water solubility = 0.03), carbofuran. (Water solubility = 0.03), mesomil (water solubility = 5.79), etiophencarb (water solubility = 0.18), acephate (water solubility = 79.0), dimethoate (water solubility = 2.5), thiocyclam Insecticides such as (water solubility = 8.0 g), pyrimicarb (water solubility = 0.3), oxamyl (water solubility = 28.0), simoxanil (water solubility = 0.1), hydroxyisoxazole (water solubility) = 8.5), metalaxyl (water solubility = 0.71), fosetyl aluminum (water solubility = 12.0), iminoctazine acetate (water solubility = 76.4) Bactericides such as Dazomet (water solubility = 0. 3), Dimethylylmol (water solubility = 0.12), Pyroxylone (water solubility = 0.4), Aloxidim (water solubility> 200), Dimetachlor (water solubility = 0.0). 2), herbicides such as cetoxydim (water solubility = 0.47), nicosulfuron (water solubility = 0.007), diquat (water solubility = 70), dichlorprop (water solubility = 0.015), daminogit ( Examples include plant growth regulators such as water solubility = 10). As the pesticidal active ingredient, one or two or more selected from the pesticidal active ingredients as exemplified above can be used. The bulking agent used in the agrochemical composition of the present invention includes 1) inorganic fine powders such as bentonite, talc, clay, diatomaceous earth, amorphous silicon dioxide, calcium carbonate, magnesium carbonate, 2) sodium sulfate, ammonium sulfate, potassium chloride, Low-molecular water-soluble compounds such as urea, 3) Sugars such as glucose, fructose, sucrose, and lactose, 4) Organic powders such as microcrystalline cellulose, wood flour, rice bran, bran, and rice straw, among others, inorganic fine powders Is preferred.
本発明の農薬組成物は、公知の方法により作製できる。例えば、１）本発明の放出制御剤、農薬活性成分、増量剤及び水を撹拌混合機を用いて混練し、その混合物を造粒機を用いて造粒して造粒物とした後、乾燥する方法、２）農薬活性成分、増量剤及び水を撹拌混合機を用いて混練し、その混合物を造粒機を用いて造粒して乾燥した後、本発明の放出制御剤を用いてコーティングする方法、３）本発明の放出制御剤、増量剤及び水を撹拌混合機を用いて混練し、その混合物を造粒機を用いて造粒物とした後、その造粒物に農薬活性成分を含浸、吸着させ、乾燥する方法等が挙げられ、いずれの方法においても各成分の混合順序を入れ替えることができる。ここで撹拌混合機としては、ナウタミキサー、リボンブレンダー、ロータリーブレンダー、Ｖ型混合機等を適用でき、また造粒機としては押出し造粒機、混合造粒機、転動造粒機、流動層造粒機等を適用できる。 The agrochemical composition of the present invention can be prepared by a known method. For example, 1) The release control agent, the agrochemical active ingredient, the extender and water of the present invention are kneaded using a stirring mixer, and the mixture is granulated using a granulator to obtain a granulated product, followed by drying. 2) Kneading an agrochemical active ingredient, an extender and water using a stirring mixer, granulating the mixture using a granulator and drying, followed by coating using the release control agent of the present invention 3) The release control agent of the present invention, the extender and water are kneaded using a stirring mixer, and the mixture is granulated using a granulator, and then the agrochemical active ingredient is added to the granulated product. The method of impregnating, adsorbing, and drying can be used, and the mixing order of each component can be changed in any method. Here, as the stirring mixer, a nauta mixer, a ribbon blender, a rotary blender, a V-type mixer, etc. can be applied, and as a granulator, an extrusion granulator, a mixing granulator, a rolling granulator, a fluidized bed A granulator or the like can be applied.
以上説明した本発明によると、農薬活性成分が水溶解度の高いものであっても優れた放出制御効果を発揮する。 According to the present invention described above, an excellent release control effect is exhibited even if the agrochemical active ingredient has high water solubility.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれら実施例に限定されるというものではない。尚、以下の実施例及び比較例において、部は質量部を、また％は質量％を意味する。 Hereinafter, examples and the like will be given in order to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.
試験区分１（ポリエステル樹脂の合成）
・ポリエステル樹脂（Ｐ−１）〜（Ｐ−４）及び（ＲＰ−１）〜（ＲＰ−４）の合成
テレフタル酸ジメチル４４．６６ｇ（０．２３モル）、イソフタル酸ジメチル２７．１９ｇ（０．１４モル）、５−スルホイソフタル酸ジメチル＝ナトリウム２０．７４ｇ（０．０７モル）、エチレングリコール５０．３ｇ（０．８１モル）、１，８−オクタンジオール１１２．６０ｇ（０．７７モル）、セバシン酸ジメチル１０３．６ｇ（０．４５モル）及びエステル交換触媒としてテトラブチルチタネート（IV）０．１５ｇを反応容器に仕込み、反応容器内を窒素置換した後、常圧下で２００℃に昇温し、副生するメタノールを留去しながら２時間エステル交換反応を行い、更に２３０℃まで昇温して２時間エステル交換反応を行った。次に２５０℃まで昇温後、徐々に反応容器内を減圧して１５分後に１００Ｐａとし、同減圧下で３０分間重縮合反応を行い、ポリエステル樹脂２００ｇを得た。このポリエステル樹脂を重クロロホルムに溶解させ、ＮＭＲ分析を行うと、構成単位Ａのテレフタル酸ジメチルから形成された構成単位を１５モル％、イソフタル酸ジメチルから形成された構成単位を８モル％、構成単位Ｂの５−スルホイソフタル酸ジメチル＝ナトリウムから形成された構成単位を２モル％、構成単位Ｃのエチレングリコールから形成された構成単位を２５モル％、構成単位Ｄの１，８−オクタンジオールから形成された構成単位を２５モル％、構成単位Ｅのセバシン酸ジメチルから形成された構成単位を２５モル％（合計１００モル％）の割合で有していて、ＧＰＣ分析を行い、標準ポリスチレンを用いた検量線から算出された数平均分子量は２５０００のものであった。これをポリエステル樹脂（Ｐ−１）とした。同様にして、表１に記載のポリエステル樹脂（Ｐ−２）〜（Ｐ−４）及び（ＲＰ−１）〜（ＲＰ−４）を合成した。
Test category 1 (synthesis of polyester resin)
Synthesis of polyester resins (P-1) to (P-4) and (RP-1) to (RP-4) 44.66 g (0.23 mol) of dimethyl terephthalate, 27.19 g of dimethyl isophthalate (0. 14 mol), dimethyl 5-sulfoisophthalate = sodium 20.74 g (0.07 mol), ethylene glycol 50.3 g (0.81 mol), 1,8-octanediol 112.60 g (0.77 mol), 103.6 g (0.45 mol) of dimethyl sebacate and 0.15 g of tetrabutyl titanate (IV) as a transesterification catalyst were charged into a reaction vessel, the inside of the reaction vessel was purged with nitrogen, and the temperature was raised to 200 ° C. under normal pressure. The ester exchange reaction was carried out for 2 hours while distilling off the by-produced methanol, and the temperature was further raised to 230 ° C. to carry out the ester exchange reaction for 2 hours. Next, after raising the temperature to 250 ° C., the pressure inside the reaction vessel was gradually reduced to 100 Pa after 15 minutes, and a polycondensation reaction was performed for 30 minutes under the reduced pressure to obtain 200 g of a polyester resin. When this polyester resin was dissolved in deuterated chloroform and subjected to NMR analysis, 15 mol% of the structural unit formed from dimethyl terephthalate as the structural unit A, 8 mol% of the structural unit formed from dimethyl isophthalate, and the structural unit 2 mol% of the structural unit formed from dimethyl 5-sulfoisophthalate of sodium B, 25 mol% of the structural unit formed from ethylene glycol of the structural unit C, formed from 1,8-octanediol of the structural unit D 25% by mole, and 25% by mole of the structural unit formed from dimethyl sebacate as the structural unit E (total 100% by mole), GPC analysis was performed, and standard polystyrene was used. The number average molecular weight calculated from the calibration curve was 25,000. This was designated as polyester resin (P-1). Similarly, polyester resins (P-2) to (P-4) and (RP-1) to (RP-4) shown in Table 1 were synthesized.
・ポリエステル樹脂（Ｐ−５）〜（Ｐ−８）及び（ＲＰ−５）、（ＲＰ−６）の合成
テレフタル酸６６．４６ｇ（０．４モル）、イソフタル酸４６．５２ｇ（０．２８モル）、エチレングリコール４４．６９ｇ（０．７２モル）、１，８−オクタンジオール１４９．１５ｇ（１．０２モル）、セバシン酸４０．４６ｇ（０．２モル）及びエステル化触媒として酢酸亜鉛（II）・二水和物０．１２ｇを反応容器に仕込み、反応容器内を窒素置換した後、窒素にて０．５ＭＰａまで加圧し、２２０℃で２時間保持した。反応容器内を徐々に常圧に戻し、副生する水を留去しながら２時間エステル化反応を行い、更に２３０℃まで昇温して１時間エステル化反応を行った。次に２６０℃まで昇温後、徐々に反応容器内を減圧して１５分後に１００Ｐａとし、同減圧下で３０分間重縮合反応を行ったところで窒素にて常圧に戻し、２３０℃まで冷却した。冷却後、トリメリット酸２５．２２ｇ（０．１２モル）を加えて反応容器を密閉し、撹拌しながら１時間解重合反応を行い、ポリエステル樹脂２００ｇを得た。このポリエステル樹脂を前記のＮＭＲ法により分析すると、構成単位Ａのテレフタル酸から形成された構成単位を２０モル％、イソフタル酸から形成された構成単位を１４モル％、構成単位Ｂのトリメリット酸から形成された構成単位を６モル％、構成単位Ｃのエチレングリコールから形成された構成単位を２０モル％、構成単位Ｄの１，８−オクタンジオールから形成された構成単位を３０モル％、構成単位Ｅのセバシン酸から形成された構成単位を１０モル％（合計１００モル％）の割合で有していて、前記のＧＰＣ法により求められた数平均分子量は４８０００のものであった。これをポリエステル樹脂（Ｐ−５）とした。同様にして、表１に記載のポリエステル樹脂（Ｐ−６）〜（Ｐ−８）及び（ＲＰ−５）、（ＲＰ−６）を合成した。
Synthesis of polyester resins (P-5) to (P-8) and (RP-5) and (RP-6) 66.46 g (0.4 mol) terephthalic acid, 46.52 g (0.28 mol) isophthalic acid ), 44.69 g (0.72 mol) of ethylene glycol, 149.15 g (1.02 mol) of 1,8-octanediol, 40.46 g (0.2 mol) of sebacic acid and zinc acetate (II) as an esterification catalyst ) · 0.12 g of dihydrate was charged into a reaction vessel, and the inside of the reaction vessel was purged with nitrogen, and then pressurized to 0.5 MPa with nitrogen and held at 220 ° C. for 2 hours. The inside of the reaction vessel was gradually returned to normal pressure, an esterification reaction was carried out for 2 hours while distilling off by-product water, and the temperature was further raised to 230 ° C. to carry out an esterification reaction for 1 hour. Next, after raising the temperature to 260 ° C., the pressure inside the reaction vessel was gradually reduced to 100 Pa after 15 minutes, and after performing a polycondensation reaction for 30 minutes under the same reduced pressure, the pressure was returned to normal pressure with nitrogen and cooled to 230 ° C. . After cooling, 25.22 g (0.12 mol) of trimellitic acid was added, the reaction vessel was sealed, and a depolymerization reaction was performed for 1 hour with stirring to obtain 200 g of a polyester resin. When this polyester resin is analyzed by the NMR method described above, the structural unit formed from the terephthalic acid of the structural unit A is 20 mol%, the structural unit formed from the isophthalic acid is 14 mol%, and the structural unit B is from trimellitic acid. 6 mol% of the structural unit formed, 20 mol% of the structural unit formed from ethylene glycol of the structural unit C, 30 mol% of the structural unit formed from 1,8-octanediol of the structural unit D, structural unit The number average molecular weight calculated | required by the said GPC method was 48000, having the structural unit formed from the sebacic acid of E in the ratio of 10 mol% (total 100 mol%). This was designated as polyester resin (P-5). Similarly, polyester resins (P-6) to (P-8), (RP-5) and (RP-6) described in Table 1 were synthesized.
表１において、
Ａ−１：テレフタル酸ジメチルから形成された構成単位
Ａ−２：テレフタル酸から形成された構成単位
Ａ−３：イソフタル酸ジメチルから形成された構成単位
Ａ−４：イソフタル酸から形成された構成単位
Ａ−５：２，６−ナフタレンジカルボン酸ジメチルから形成された構成単位
Ａ−６：２，６−ナフタレンジカルボン酸から形成された構成単位
Ｂ−１：５−スルホイソフタル酸ジメチル＝ナトリウムから形成された構成単位
Ｂ−２：トリメリット酸から形成された構成単位
Ｂ−３：ピロメリット酸から形成された構成単位
Ｃ−１：エチレングリコールから形成された構成単位
Ｃ−２：１，３−プロパンジオールから形成された構成単位
Ｄ−１：１，８−オクタンジオールから形成された構成単位
Ｄ−２：１，６−ヘキサンジオールから形成された構成単位
Ｄ−３：ネオペンチルグリコールから形成された構成単位
Ｄ−４：１，４−ブタンジオールから形成された構成単位
Ｄ−５：ジエチレングリコールから形成された構成単位
Ｄ−６：ポリテトラメチレングリコール（Ｍｗ＝１０００）から形成された構成単位
Ｄ−７：ポリエチレングリコール（Ｍｗ＝３４００）から形成された構成単位
Ｅ−１：セバシン酸ジメチルから形成された構成単位
Ｅ−２：セバシン酸から形成された構成単位
Ｅ−３：アジピン酸ジメチルから形成された構成単位
Ｅ−４：アジピン酸から形成された構成単位
In Table 1,
A-1: Structural unit formed from dimethyl terephthalate A-2: Structural unit formed from terephthalic acid A-3: Structural unit formed from dimethyl isophthalate A-4: Structural unit formed from isophthalic acid A-5: Structural unit formed from dimethyl 2,6-naphthalenedicarboxylate A-6: Structural unit formed from 2,6-naphthalenedicarboxylic acid B-1: Formed from dimethyl 5-sulfoisophthalate = sodium B-2: a structural unit formed from trimellitic acid B-3: a structural unit formed from pyromellitic acid C-1: a structural unit formed from ethylene glycol C-2: 1,3-propane Structural unit formed from diol D-1: Structural unit formed from 1,8-octanediol D-2: 1,6-hexanedio D-3: Structural unit formed from neopentyl glycol D-4: Structural unit formed from 1,4-butanediol D-5: Structural unit formed from diethylene glycol D-6: Structural unit formed from polytetramethylene glycol (Mw = 1000) D-7: Structural unit formed from polyethylene glycol (Mw = 3400) E-1: Structural unit formed from dimethyl sebacate E-2: Sebacin Structural unit formed from acid E-3: Structural unit formed from dimethyl adipate E-4: Structural unit formed from adipic acid
試験区分２（ポリエステル樹脂エマルションの調製）
・ポリエステル樹脂（Ｐ−１）〜（Ｐ−４）及び（ＲＰ−１）〜（ＲＰ−４）のエマルションの調製
試験区分１で合成したポリエステル樹脂（Ｐ−１）４０部及びテトラヒドロフラン１０５部を容器に仕込み、室温で混合して均一溶液とした。次に、この均一溶液を室温で撹拌しながら、これに室温の水１２０部を徐々に滴下して、ポリエステル樹脂−テトラヒドロフラン−水の分散系を得た。さらにこの分散系を撹拌しながら、容器内を常圧下にて６０〜８０℃とし、テトラヒドロフランを留去して、ポリエステル樹脂（Ｐ−１）の固形分濃度２５％のエマルションを得た。同様にして、ポリエステル樹脂（Ｐ−２）〜（Ｐ−４）及び（ＲＰ−１）、（ＲＰ−２）の固形分濃度２５％のエマルションを調製した。ポリエステル樹脂（ＲＰ−３）及び（ＲＰ−４）についても同様にエマルションの調製を試みたが、乳化せず、エマルションを調製できなかった。
Test Category 2 (Preparation of polyester resin emulsion)
Preparation of emulsions of polyester resins (P-1) to (P-4) and (RP-1) to (RP-4) 40 parts of polyester resin (P-1) synthesized in Test Category 1 and 105 parts of tetrahydrofuran The solution was charged into a container and mixed at room temperature to obtain a uniform solution. Next, while stirring the homogeneous solution at room temperature, 120 parts of water at room temperature was gradually added dropwise to obtain a polyester resin-tetrahydrofuran-water dispersion. Furthermore, stirring this dispersion, the inside of a container was made into 60-80 degreeC under normal pressure, tetrahydrofuran was distilled off, and the emulsion with a solid content concentration of 25% of the polyester resin (P-1) was obtained. Similarly, emulsions with a solid content concentration of 25% of polyester resins (P-2) to (P-4), (RP-1), and (RP-2) were prepared. For the polyester resins (RP-3) and (RP-4), an attempt was made to prepare an emulsion in the same manner, but the emulsion was not emulsified and the emulsion could not be prepared.
・ポリエステル樹脂（Ｐ−５）〜（Ｐ−８）及び（ＲＰ−５）、（ＲＰ−６）のエマルションの調製
純水２４０部及びイソプロピルアルコール６０部を容器に仕込み、撹拌しながら、試験区分１で合成したポリエステル樹脂（Ｐ−５）１００部を投入した。次にこのポリエステル樹脂の酸価に対して１．５倍当量の２５％アンモニア水４部を投入して、ポリエステル樹脂−イソプロピルアルコール−水の分散系とした。さらにこの分散系を撹拌しながら、容器内を常圧下にて８０℃まで加温し、イソプロピルアルコールを留去した。留去はイソプロピルアルコールの１．５倍量のイソプロピルアルコールと水との混合物を回収して終了した。留去後、容器内を２０℃まで冷却して、ポリエステル樹脂（Ｐ−５）の固形分濃度３０％のエマルションを得た。同様にして、ポリエステル樹脂（Ｐ−６）〜（Ｐ−８）及び（ＲＰ−５）の固形分濃度３０％のエマルションを調製した。ポリエステル樹脂（ＲＰ−６）についても同様にエマルションの調製を試みたが、乳化せず、エマルションを調製できなかった。
-Preparation of emulsions of polyester resins (P-5) to (P-8) and (RP-5), (RP-6) Charge 240 parts of pure water and 60 parts of isopropyl alcohol into a container and stir while stirring. 100 parts of the polyester resin (P-5) synthesized in 1 was added. Next, 4 parts of 25% ammonia water equivalent to 1.5 times the acid value of the polyester resin was added to obtain a polyester resin-isopropyl alcohol-water dispersion. Further, while stirring this dispersion, the inside of the container was heated to 80 ° C. under normal pressure to distill off isopropyl alcohol. Distillation was completed by collecting a mixture of isopropyl alcohol and water in an amount 1.5 times that of isopropyl alcohol. After the distillation, the inside of the container was cooled to 20 ° C. to obtain an emulsion having a polyester resin (P-5) concentration of 30%. In the same manner, emulsions of polyester resins (P-6) to (P-8) and (RP-5) with a solid content concentration of 30% were prepared. For the polyester resin (RP-6), an attempt was similarly made to prepare an emulsion, but the emulsion was not emulsified and could not be prepared.
試験区分３（農薬活性成分放出制御剤及び徐放性農薬組成物の調製）
・実施例１〜５、１５，１６及び比較例１〜９
試験区分２で調製したポリエステル樹脂（Ｐ−１）の固形分濃度２５％のエマルション２００部（固形分として５０部）とカルナバワックスの固形分濃度３０％のエマルション１６６．７部（固形分として５０部）とを混合し、実施例１の農薬活性成分放出制御剤を調製した。次に農薬活性成分としてピメトロジン８０部、増量剤としてクレー６２０部、珪藻土２００部を混合した後、前記で調製した実施例１の農薬活性成分放出制御剤１００部を添加して徐放性農薬組成物を調製した。これに適量の水を加えて十分混練し、その混練物を目開き１．２ｍｍのスクリーンを装着したバスケット型造粒器（筒井理化学器械社製のＫＡＲ−７５形）に供し、押出し成形した。押出し成形物を２〜４ｍｍの長さに切断した後、１０５℃の恒温器にて２時間乾燥し、農薬粒剤を製造した。同様にして、表２に記載の実施例２〜５、１５、１６及び表３に記載の比較例１〜９の農薬活性成分放出制御剤を調製し、更に徐放性農薬組成物を調製して、農薬粒剤を製造した。
Test Category 3 (Preparation of active ingredient release control agent and sustained release agricultural chemical composition)
Examples 1 to 5, 15, 16 and Comparative Examples 1 to 9
200 parts of a 25% solids emulsion of polyester resin (P-1) prepared in Test Category 2 (50 parts as solids) and 166.7 parts of a 30% solids concentration of carnauba wax (50 as solids) Part) was mixed to prepare an agricultural chemical active ingredient release controlling agent of Example 1. Next, 80 parts of pymetrozine as an agrochemical active ingredient, 620 parts of clay as an extender, and 200 parts of diatomaceous earth were mixed, and then 100 parts of the pesticidal active ingredient release control agent of Example 1 prepared above was added to provide a sustained release agrochemical composition. A product was prepared. An appropriate amount of water was added thereto and kneaded sufficiently, and the kneaded product was subjected to a basket type granulator equipped with a screen having a mesh opening of 1.2 mm (KAR-75 type manufactured by Tsutsui Rika Kikai Co., Ltd.) and extruded. The extruded product was cut to a length of 2 to 4 mm and then dried for 2 hours in a thermostat at 105 ° C. to produce agrochemical granules. Similarly, the agricultural chemical active ingredient release control agents of Examples 2 to 5, 15, 16 and Comparative Examples 1 to 9 described in Table 2 were prepared, and further a sustained release agricultural chemical composition was prepared. Agrochemical granules were manufactured.
・実施例６〜１４、１７及び比較例１０〜１６
試験区分２で調製したポリエステル樹脂（Ｐ−１）の固形分濃度２５％のエマルション２８０部（固形分として７０部）とカルナバワックスの固形分濃度３０％のエマルション１００部（固形分として３０部）とを混合し、実施例６の農薬活性成分放出制御剤を調製した。次に調製した実施例６の農薬活性成分放出制御剤１００部、農薬活性成分としてピメトロジン６０部を混合した後、増量剤として珪藻土３４０部を混合し、徐放性農薬組成物を調製した。これに適量の水を加えて十分混練し、その混練物を目開き１．２ｍｍのスクリーンを装着したバスケット型造粒器（筒井理化学器械社製のＫＡＲ−７５形）に供し、押出し成形した。押出し成形物を２〜４ｍｍの長さに切断した後、１０５℃の恒温器にて２時間乾燥し、農薬粒剤を製造した。同様にして、表２に記載の実施例７〜１４、１７及び表３に記載の比較例１０〜１６の農薬活性成分放出制御剤を調製し、更に徐放性農薬組成物を調製して、農薬粒剤を製造した。
Examples 6 to 14 and 17 and Comparative Examples 10 to 16
280 parts of an emulsion with a solid content concentration of 25% of the polyester resin (P-1) prepared in Test Category 2 (70 parts as a solid content) and 100 parts of an emulsion with a solid content concentration of carnauba wax of 30% (30 parts as a solid content) And an agrochemical active ingredient release controlling agent of Example 6 were prepared. Next, 100 parts of the prepared agricultural chemical active ingredient release controlling agent of Example 6 and 60 parts of pymetrozine as an agricultural chemical active ingredient were mixed, and then 340 parts of diatomaceous earth was mixed as an extender to prepare a sustained release agricultural chemical composition. An appropriate amount of water was added thereto and kneaded sufficiently, and the kneaded product was subjected to a basket type granulator equipped with a screen having a mesh opening of 1.2 mm (KAR-75 type manufactured by Tsutsui Rika Kikai Co., Ltd.) and extruded. The extruded product was cut to a length of 2 to 4 mm and then dried for 2 hours in a thermostat at 105 ° C. to produce agrochemical granules. Similarly, the pesticidal active ingredient release control agents of Examples 7 to 14 and 17 described in Table 2 and Comparative Examples 10 to 16 described in Table 3 were prepared, and further a sustained release agricultural chemical composition was prepared. Agrochemical granules were produced.
・実施例１８及び比較例１７、１８
農薬活性成分としてピメトロジン４０部、増量剤としてクレー７６０部、ベントナイト１００部を混合した。これに適量の水を加えて十分混練し、その混練物を目開き１．２ｍｍのスクリーンを装着したバスケット型造粒器（筒井理化学器械社製のＫＡＲ−７５形）に供し、押出し成形した。押出し成形物を２〜４ｍｍの長さに切断した後、５４℃の恒温器にて４時間乾燥した。次にパン型造粒器（アズワン社製、ＤＰＺ−０１型）へ乾燥物を投入し、４０〜５０℃にて転動させながら、試験区分２で調製したポリエステル樹脂の固形分濃度２５％のエマルション（Ｐ−７）をスプレーした。被覆量がポリエステル樹脂（Ｐ−７）の固形分として１００部となるまでスプレーと乾燥を繰り返し、徐放性農薬組成物を調製すると同時に農薬粒剤を製造した。同様にして、表３に記載の比較例１７及び１８の徐放性農薬組成物を調製し、同時に農薬粒剤を製造した。
Example 18 and Comparative Examples 17 and 18
40 parts of pymetrozine as an agrochemical active ingredient, 760 parts of clay as a bulking agent, and 100 parts of bentonite were mixed. An appropriate amount of water was added thereto and kneaded sufficiently, and the kneaded product was subjected to a basket type granulator equipped with a screen having a mesh opening of 1.2 mm (KAR-75 type manufactured by Tsutsui Rika Kikai Co., Ltd.) and extruded. The extruded product was cut to a length of 2 to 4 mm and then dried for 4 hours in a 54 ° C. incubator. Next, the dried product was put into a bread granulator (manufactured by ASONE, DPZ-01 type) and rolled at 40 to 50 ° C., while the polyester resin prepared in Test Category 2 had a solid content concentration of 25%. The emulsion (P-7) was sprayed. Spraying and drying were repeated until the coating amount became 100 parts as a solid content of the polyester resin (P-7) to prepare a sustained-release agricultural chemical composition, and at the same time, agricultural chemical granules were produced. Similarly, the sustained release agricultural chemical compositions of Comparative Examples 17 and 18 shown in Table 3 were prepared, and at the same time, agricultural chemical granules were produced.
試験区分４（農薬粒剤の評価）
・溶出率の評価
溶出試験器（宮本理研工業社製のＰＪ−６２Ｎ型）のフラスコにイオン交換水１０００ｇを量りとり、水槽温度を４０℃、シャフト回転速度を４０ｒｐｍに設定した。水槽温度が４０℃に達した時点で、シャフトを停止させ、試験区分３で製造した農薬粒剤２００ｍｇを投入した。１時間後及び４時間後にフラスコ中心部より採水し、その採取した水中の農薬活性成分濃度を液体クロマトグラフィーで測定して、溶出した農薬活性成分量を算出した。供試した農薬粒剤中の農薬活性成分が完全に溶出した場合の濃度を溶出率１００％として溶出率を算出し、下記の基準で評価した。
◎：溶出率が３５％未満
○：溶出率が３５％以上５５％未満
△：溶出率が５５％以上７５％未満
×：溶出率が７５％以上
××：溶出率が９０％以上
Test Category 4 (Evaluation of agricultural chemical granules)
Evaluation of dissolution rate 1000 g of ion-exchanged water was weighed into a flask of a dissolution tester (PJ-62N type manufactured by Miyamoto Riken Kogyo Co., Ltd.), the water bath temperature was set to 40 ° C., and the shaft rotation speed was set to 40 rpm. When the water bath temperature reached 40 ° C., the shaft was stopped, and 200 mg of the agrochemical granule produced in Test Category 3 was added. After 1 hour and 4 hours, water was collected from the center of the flask, and the concentration of the agrochemical active ingredient in the collected water was measured by liquid chromatography, and the amount of the eluted agrochemical active ingredient was calculated. The elution rate was calculated with the concentration at the time when the pesticide active ingredient in the tested pesticide granules was completely eluted as the elution rate of 100%, and evaluated according to the following criteria.
◎: Elution rate is less than 35% ○: Elution rate is 35% or more and less than 55% △: Elution rate is 55% or more and less than 75% ×: Elution rate is 75% or more XX: Elution rate is 90% or more
表２及び表３において、
Ｐ−１〜Ｐ−８，ＲＰ−１，ＲＰ−２，ＲＰ−５：表１に記載のポリエステル樹脂
Ｈ−１：カルナバワックスエマルション（融点：８５℃）
Ｈ−２：酢酸ビニルの固形分濃度５５％のエマルション（Ｔｇ：３０℃）
Ｈ−３：ウレタン樹脂の固形分濃度３０％のエマルション（Ｔｇ：４０℃）
Ｈ−４：オレフィン樹脂の固形分濃度３０％のエマルション（Ｔｇ：２０℃）
Ｈ−５：ベヘニルリン酸＝カリウムの固形分濃度２８％のエマルション
Ｈ−６：粉末カルナバワックス（融点：８５℃）
Ｈ−７：ポリ乳酸樹脂（融点：１６５℃）
Ｉ−１：ピメトロジン（水溶解度２７０ｐｐｍ）
Ｊ−１：クレー
Ｊ−２：珪藻土
Ｊ−３：ベントナイト
Ｋ−１：キサンタンガム
Ｋ−２：カルボキシメチルセルロース
Ｋ−３：ポリオキシエチレンオクチルエーテルホスフェート塩
In Table 2 and Table 3,
P-1 to P-8, RP-1, RP-2, RP-5: Polyester resin described in Table 1 H-1: Carnauba wax emulsion (melting point: 85 ° C.)
H-2: Vinyl acetate emulsion having a solid content concentration of 55% (Tg: 30 ° C.)
H-3: Emulsion with a solid content concentration of urethane resin of 30% (Tg: 40 ° C.)
H-4: Emulsion with solid content concentration of olefin resin of 30% (Tg: 20 ° C.)
H-5: emulsion of behenyl phosphate = potassium solid concentration 28% H-6: powdered carnauba wax (melting point: 85 ° C.)
H-7: Polylactic acid resin (melting point: 165 ° C.)
I-1: Pymetrozine (water solubility 270 ppm)
J-1: Clay J-2: Diatomaceous earth J-3: Bentonite K-1: Xanthan gum K-2: Carboxymethylcellulose K-3: Polyoxyethylene octyl ether phosphate salt
Claims (5)
構成単位Ａ：炭素数８〜１２の芳香族ジカルボン酸から形成された構成単位及び／又は炭素数８〜１２の芳香族ジカルボン酸のエステル形成性誘導体から形成された構成単位
構成単位Ｂ：分子中にスルホン酸塩基を有する炭素数８〜１２の芳香族ジカルボン酸の塩から形成された構成単位、分子中にスルホン酸塩基を有する炭素数８〜１２の芳香族ジカルボン酸のエステル形成性誘導体の塩から形成された構成単位、炭素数９〜２０の３又は４価の芳香族ポリカルボン酸から形成された構成単位及び炭素数９〜２０の３又は４価の芳香族ポリカルボン酸のエステル形成性誘導体から形成された構成単位から選ばれる一つ又は二つ以上
構成単位Ｃ：エチレングリコールから形成された構成単位及び／又はプロピレングリコールから形成された構成単位
構成単位Ｄ：炭素数４〜１０のジオールから形成された構成単位及び／又は分子中に炭素数２〜４のオキシアルキレン単位で構成されたポリオキシアルキレン基を有する分子量４００〜５０００のポリアルキレングリコールから形成された構成単位
構成単位Ｅ：炭素数４〜２２の脂肪族ジカルボン酸から形成された構成単位及び／又は炭素数４〜２２の脂肪族ジカルボン酸のエステル形成性誘導体から形成された構成単位 The following structural unit A is 9-48.5 mol%, the following structural unit B is 0.5-30 mol%, the following structural unit C is 5-48 mol%, and the following structural unit D is 2-45 mol%. % And the following structural unit E is composed of a ratio of 1 to 40 mol% (total 100 mol%), and contains a polyester resin having a number average molecular weight of 5000 to 100,000. Release control agent.
Structural unit A: a structural unit formed from an aromatic dicarboxylic acid having 8 to 12 carbon atoms and / or a structural unit formed from an ester-forming derivative of an aromatic dicarboxylic acid having 8 to 12 carbon atoms Structural unit B: in the molecule A structural unit formed from a salt of an aromatic dicarboxylic acid having 8 to 12 carbon atoms having a sulfonate group in the above, a salt of an ester-forming derivative of an aromatic dicarboxylic acid having 8 to 12 carbon atoms having a sulfonate group in the molecule , A structural unit formed from a tri- or tetravalent aromatic polycarboxylic acid having 9 to 20 carbon atoms and an ester forming property of a tri- or tetravalent aromatic polycarboxylic acid having 9 to 20 carbon atoms One or more selected from structural units formed from derivatives Structural unit C: formed from ethylene glycol and / or propylene glycol Constituent Unit Constituent Unit D: A polyunit having a molecular weight of 400 to 5000 having a constituent unit formed from a diol having 4 to 10 carbon atoms and / or a polyoxyalkylene group having a oxyalkylene unit having 2 to 4 carbon atoms in the molecule. Structural unit formed from alkylene glycol Structural unit E: formed from an aliphatic dicarboxylic acid having 4 to 22 carbon atoms and / or an ester-forming derivative of an aliphatic dicarboxylic acid having 4 to 22 carbon atoms Composition unit
樹脂：ポリ酢酸ビニル、酢酸ビニル-エチレン共重合物、ポリウレタン及びポリオレフィンから選ばれる一つ又は二つ以上
ワックス：カルナバワックス、パラフィンワックス、ヒマシ硬化油、菜種硬化油及びパーム硬化油から選ばれる一つ又は二つ以上 The active ingredient release control agent for agricultural chemicals according to claim 1, further comprising one or more selected from the following resins, the following waxes, organophosphates and salts of organophosphates.
Resin: One or more selected from polyvinyl acetate, vinyl acetate-ethylene copolymer, polyurethane and polyolefin Wax: One selected from carnauba wax, paraffin wax, castor oil, rapeseed oil and palm oil Or two or more
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