JPH101403A - Agrochemical granular agent composition - Google Patents
Agrochemical granular agent compositionInfo
- Publication number
- JPH101403A JPH101403A JP15109496A JP15109496A JPH101403A JP H101403 A JPH101403 A JP H101403A JP 15109496 A JP15109496 A JP 15109496A JP 15109496 A JP15109496 A JP 15109496A JP H101403 A JPH101403 A JP H101403A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- parts
- michael addition
- modified
- modified polyvinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title abstract description 14
- 239000003905 agrochemical Substances 0.000 title abstract description 9
- 239000003795 chemical substances by application Substances 0.000 title abstract 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 45
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 45
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
- 239000000575 pesticide Substances 0.000 claims description 19
- 239000008202 granule composition Substances 0.000 claims description 17
- 230000000361 pesticidal effect Effects 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 125000002348 vinylic group Chemical group 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000008187 granular material Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 14
- 238000012986 modification Methods 0.000 description 13
- 230000004048 modification Effects 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000007127 saponification reaction Methods 0.000 description 9
- 239000007884 disintegrant Substances 0.000 description 6
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 4
- -1 sulfosuccinate soda salts Chemical class 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、農薬原体を無機鉱
物担体等と混合して粒状形態の農薬を製造する際に用い
る農薬粒剤組成物に関する。TECHNICAL FIELD The present invention relates to a pesticide granule composition used for producing a pesticide in a granular form by mixing a pesticide bulk with an inorganic mineral carrier or the like.
【０００２】[0002]
【従来の技術】農薬の製剤には、粉剤、乳剤、水和剤、
粒剤、フロアブル等の剤型があり、農薬の使用目的によ
り選択されている。2. Description of the Related Art Agrochemical formulations include powders, emulsions, wettable powders,
There are dosage forms such as granules and flowables, which are selected according to the purpose of use of the pesticide.
【０００３】上記のうち粒剤は、粉末の飛散が無く、取
り扱いやすく、省力化が可能であることから、除草剤、
殺虫剤などに広く使用されている。[0003] Among the above, granules are herbicides, because they do not scatter powder, are easy to handle and can save labor.
Widely used for insecticides.
【０００４】農薬粒剤は、農薬原体、ベントナイト、炭
酸カルシウム、クレー、タルク、カオリン等の無機鉱物
を必須成分とし、粘結剤及び／又は崩壊剤を必要に応じ
て含有する。粘結剤としては、澱粉、ポリビニルアルコ
ール、ゼラチン、カルボキシメチルセルロース、アルギ
ン酸ソーダ等が使用され、また、崩壊剤としては、トリ
ポリリン酸ソーダ、ピロリン酸ソーダ等の無機塩、ポリ
エチレングリコールノニルフェニルエーテル（ＨＬＢ＝
１２〜１４）、ジアルキルスルホコハク酸エステルソー
ダ塩等の界面活性剤、また特公昭４８−１５０１号公報
に記載されているような、不飽和モノカルボン酸、不飽
和ジカルボン酸からなる重合体が使用されている。[0004] The pesticide granules contain an inorganic pesticide, bentonite, calcium carbonate, clay, talc, kaolin and other inorganic minerals as essential components, and contain a binder and / or a disintegrant as required. As the binder, starch, polyvinyl alcohol, gelatin, carboxymethylcellulose, sodium alginate and the like are used. As the disintegrant, inorganic salts such as sodium tripolyphosphate and sodium pyrophosphate, polyethylene glycol nonylphenyl ether (HLB =
12-14), surfactants such as dialkyl sulfosuccinate soda salts, and polymers comprising unsaturated monocarboxylic acids and unsaturated dicarboxylic acids as described in JP-B-48-1501. ing.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、前述し
た粘結剤、崩壊剤には、次のような問題点がある。However, the above-mentioned binders and disintegrators have the following problems.
【０００６】即ち、ポリビニルアルコール、ゼラチンを
粘結剤とした粒剤は、輸送時の耐崩壊性は良好である
が、水中での崩壊性は極めて不良である。水中崩壊性を
改良する目的で崩壊剤を配合しても、バインダー力が強
すぎて効果は期待できない。[0006] That is, granules using polyvinyl alcohol and gelatin as binders have good disintegration resistance during transportation, but extremely poor disintegration in water. Even if a disintegrant is blended for the purpose of improving disintegration in water, the effect cannot be expected because the binder power is too strong.
【０００７】また、澱粉、カルボキシメチルセルロー
ス、アルギン酸ソーダを粘結剤とした粒剤は、輸送時に
崩壊し易く、水中崩壊性も悪い。このため、崩壊剤を併
用しなければならない。[0007] Granules using starch, carboxymethylcellulose, and sodium alginate as binders are easily disintegrated during transportation and have poor disintegration properties in water. For this reason, a disintegrant must be used in combination.
【０００８】一方、無機塩、界面活性剤を崩壊剤とした
粒剤は、粘結性がないため粉化し易く、従って、粘結剤
を併用しなければならない。On the other hand, granules using an inorganic salt or a surfactant as a disintegrant have no caking properties and are easily powdered. Therefore, a binder must be used in combination.
【０００９】また、前記した特公昭４８−１５０１号公
報明細書に記載されている重合体を用いたものは、水中
崩壊性は有するが、脆すぎて使用することができない。A polymer using the polymer described in JP-B-48-1501 has disintegration properties in water, but is too brittle to be used.
【００１０】さらに、水中崩壊性と硬度を改善した農薬
粒剤組成物として、ポリビニルアルコールあるいはポリ
ビニルアルコール変性物のモノクロール酢酸反応物を配
合することが提案されているが（特開昭５７−１５４１
０４号公報）、硬度と水中崩壊性がなお不充分である。Furthermore, as an agricultural chemical granule composition having improved disintegration property in water and hardness, it has been proposed to blend polyvinyl alcohol or a monochloroacetic acid reactant of polyvinyl alcohol modified product (JP-A-57-1541).
No. 04), the hardness and disintegration in water are still insufficient.
【００１１】本発明は上記に鑑みてなされたものであ
り、輸送時の振動や手荒な取扱いなどによっては崩壊し
ない硬度を有し、しかも水中に投入した場合には速やか
に崩壊拡散し、農薬効果を最大限に発揮することを可能
にする農薬粒剤組成物を提供するものである。[0011] The present invention has been made in view of the above, has a hardness that does not collapse due to vibration during transportation and rough handling, and quickly disintegrates and disperses when put into water, and has a pesticidal effect. The present invention provides a pesticidal granule composition capable of maximizing the effect.
【００１２】[0012]
【課題を解決するための手段】本発明者らは鋭意検討の
結果、農薬原体及び無機鉱物担体を必須成分とする農薬
粒剤組成物に、ポリビニルアルコールに１種または２種
以上のビニル化合物をマイケル付加して、あるいはマイ
ケル付加したのち一部又は完全に加水分解して得られる
ノニオン及び／またはアニオン変性ポリビニルアルコー
ルを配合することによって、輸送時に崩壊しない硬度を
有し、しかも水中崩壊性の良好な農薬粒剤組成物を調製
できることを見いだし、本発明に到達した。Means for Solving the Problems As a result of intensive studies, the present inventors have found that one or two or more vinyl compounds can be added to polyvinyl alcohol in a pesticide granule composition containing a pesticide bulk material and an inorganic mineral carrier as essential components. By adding nonionic and / or anion-modified polyvinyl alcohol obtained by adding Michael or partially or completely hydrolyzing after adding Michael, has a hardness that does not disintegrate during transportation, and has a disintegration property in water. The present inventors have found that a good pesticide granule composition can be prepared, and have reached the present invention.
【００１３】すなわち、請求項１の農薬粒剤組成物は、
上記の課題を解決するために、ポリビニルアルコールに
１種または２種以上のビニル化合物をマイケル付加して
得られる、あるいはマイケル付加したのち一部又は完全
に加水分解して得られる、ノニオン変性及び／又はアニ
オン変性ポリビニルアルコールを配合してなるものであ
る。That is, the pesticidal granule composition of claim 1 is
In order to solve the above-mentioned problem, nonionic modified and / or obtained by Michael addition of one or more vinyl compounds to polyvinyl alcohol, or obtained by partially or completely hydrolyzing after adding Michael. Alternatively, it is obtained by blending an anion-modified polyvinyl alcohol.
【００１４】請求項１の農薬粒剤組成物に配合されるノ
ニオン変性及び／又はアニオン変性ポリビニルアルコー
ルとして、請求項２では、ポリビニルアルコールにアク
リロニトリル又はアクリルアミドをマイケル付加して、
あるいはマイケル付加したのち一部又は完全に加水分解
して得られるものを用い、請求項３では、ポリビニルア
ルコール又は請求項２の変性ポリビニルアルコールに２
−アクリルアミド−２−メチルプロパン−３−スルホン
酸あるいはその塩をマイケル付加して得られるものを用
いる。The nonionic and / or anion-modified polyvinyl alcohol to be added to the pesticide granule composition of claim 1 is the method of claim 2, wherein acrylonitrile or acrylamide is added to the polyvinyl alcohol by Michael.
Alternatively, a product obtained by partially or completely hydrolyzing after Michael addition is used. In claim 3, the polyvinyl alcohol or the modified polyvinyl alcohol in claim 2 is used.
-Acrylamide-2-methylpropane-3-sulfonic acid or a salt thereof obtained by Michael addition is used.
【００１５】[0015]
【発明の実施の形態】本発明に用いられる変性ポリビニ
ルアルコールは、ポリビニルアルコール（以下ＰＶＡと
いう）に１種または２種以上のビニル化合物をマイケル
付加して、あるいはマイケル付加した後、一部又は完全
に加水分解して得ることができる。BEST MODE FOR CARRYING OUT THE INVENTION The modified polyvinyl alcohol used in the present invention is obtained by adding one or more vinyl compounds to polyvinyl alcohol (hereinafter referred to as PVA) by Michael, or after adding Michael, partially or completely. Can be obtained by hydrolysis.
【００１６】変性ＰＶＡの重合度は、特に限定されない
が、２００〜８，０００が好ましく、３００〜４，００
０がより好ましい。重合度が２００未満であると十分な
バインダー力が得られない場合があり、８，０００を越
えるとバインダー力が強過ぎて農薬粒剤組成物の水中崩
壊分散性が悪くなる場合がある。The degree of polymerization of the modified PVA is not particularly limited, but is preferably from 200 to 8,000, more preferably from 300 to 4,000.
0 is more preferred. If the degree of polymerization is less than 200, sufficient binder power may not be obtained in some cases, and if it exceeds 8,000, the binder power is too strong, and the disintegration / disintegration in water of the agricultural chemical granule composition may be poor.
【００１７】また、ノニオン性及び／またはアニオン性
基の変性率としては、２．０〜４０モル％が好ましく、
４．０〜３０モル％がより好ましい。２．０モル％未満
であると変性ポリビニルアルコールの水溶解性が悪化
し、農薬粒剤組成物の水中崩壊分散性が悪くなる。一
方、４０モル％を越えるものは、製造が困難であるばか
りでなくコストが高くつく。The modification rate of the nonionic and / or anionic groups is preferably 2.0 to 40 mol%.
4.0-30 mol% is more preferable. If the amount is less than 2.0 mol%, the water solubility of the modified polyvinyl alcohol is deteriorated, and the disintegration and dispersibility in water of the pesticidal granule composition is deteriorated. On the other hand, those exceeding 40 mol% are not only difficult to produce but also costly.
【００１８】ＰＶＡにマイケル付加した後、ノニオン性
を示すビニル化合物としては、アクリロニトリル、アク
リルアミド等が挙げられる。アニオン性を示すビニル化
合物としては、２−アクリルアミド−２−メチルプロパ
ン−３−スルホン酸（塩）（以下ＡＭＰＳという）等が
挙げられる。アクリロニトリル、アクリルアミドは、マ
イケル付加反応後、アルカリで完全に加水分解すること
によって、アニオン性を示すカルボキシエチル基に変性
することもできる。また、一部加水分解することによ
り、アニオン性基（カルボキシル基）とノニオン性基
（アミド基）の両方を有する変性ＰＶＡとすることもで
きる。After the addition of Michael to PVA, vinyl compounds exhibiting nonionic properties include acrylonitrile, acrylamide and the like. Examples of the anionic vinyl compound include 2-acrylamido-2-methylpropane-3-sulfonic acid (salt) (hereinafter referred to as AMPS). After the Michael addition reaction, acrylonitrile and acrylamide can be completely hydrolyzed with an alkali to be modified into an anionic carboxyethyl group. Further, by partially hydrolyzing, a modified PVA having both an anionic group (carboxyl group) and a nonionic group (amide group) can be obtained.
【００１９】原料ＰＶＡとしては、完全けん化ＰＶＡの
ほか、部分けん化ＰＶＡも使用可能である。また、酢酸
ビニルと共重合可能なモノマー、例えば、イタコン酸、
ＡＭＰＳ等と共重合後けん化させて得られる変性ＰＶＡ
も使用できる。As the raw material PVA, partially saponified PVA can be used in addition to completely saponified PVA. Further, a monomer copolymerizable with vinyl acetate, for example, itaconic acid,
Modified PVA obtained by saponification after copolymerization with AMPS etc.
Can also be used.
【００２０】本発明で用いられる上記変性ＰＶＡの例と
して、次の〜の各変性ＰＶＡの構造式を示す。As examples of the modified PVA used in the present invention, the following structural formulas of the modified PVA are shown.
【００２１】ＰＶＡにアクリルアミドをマイケル付加
したもの：Acrylic amide added to PVA by Michael:
【化１】 。Embedded image .
【００２２】ＰＶＡにアクリルアミドをマイケル付加
後、完全に加水分解したもの：[0022] PVA is completely hydrolyzed after addition of acrylamide to Michael:
【化２】 。Embedded image .
【００２３】ＰＶＡにアクリルアミドをマイケル付加
後、一部加水分解したもの：[0023] PVA is partially hydrolyzed after Michael addition of acrylamide to:
【化３】 。Embedded image .
【００２４】ＰＶＡにＡＭＰＳをマイケル付加したも
の：[0024] PVA with Michael added to AMPS:
【化４】 。Embedded image .
【００２５】ＰＶＡにアクリルアミドをマイケル付加
し加水分解した後、ＡＭＰＳをマイケル付加したもの：Acrylic addition of acrylamide to PVA followed by hydrolysis, followed by addition of AMPS to Michael:
【化５】 。Embedded image .
【００２６】本発明の農薬粒剤組成物における上記変性
ＰＶＡの使用量は、０．０５〜８．０重量％の範囲が望
ましい。０．０５％未満であると満足できるバインダー
力が得られにくく、また、８．０％を越えるとコストが
高くつくばかりでなく、農薬粒剤の水中崩壊分散性が悪
くなる。The amount of the modified PVA used in the pesticidal granule composition of the present invention is preferably in the range of 0.05 to 8.0% by weight. If it is less than 0.05%, a satisfactory binder power is hardly obtained, and if it exceeds 8.0%, not only the cost is high but also the disintegration and disintegration of the pesticide granules in water is deteriorated.
【００２７】本発明の農薬粒剤組成物においては、上記
変性ＰＶＡをバインダー成分として単独で使用するほ
か、ＣＭＣ等の既存のバインダーを併用してもよい。In the pesticidal granule composition of the present invention, the above-mentioned modified PVA may be used alone as a binder component, or an existing binder such as CMC may be used in combination.
【００２８】[0028]
【実施例】以下、実施例によって本発明を更に詳細に説
明する。なお、文中、部または％とあるものは、特に断
りのない限り重量基準である。The present invention will be described in more detail with reference to the following examples. In the following description, parts and% are based on weight unless otherwise specified.
【００２９】製造例１ ４リットル容の横形ブレンダーにＰＶＡ（重合度２，５
００、けん化度９８．８モル％）４４０部、３０％−Ｎ
ａＯＨ水溶液２００部、及び５０％−アクリルアミド水
溶液４８４部を加え、６０℃で８時間攪拌した。次いで
５０％−ＮａＯＨ１００部を加え、９０℃で１時間加水
分解を行った。 Production Example 1 PVA (degree of polymerization 2.5, 5) was placed in a 4-liter horizontal blender.
00, degree of saponification 98.8 mol%) 440 parts, 30% -N
200 parts of an aOH aqueous solution and 484 parts of a 50% -acrylamide aqueous solution were added, and the mixture was stirred at 60 ° C for 8 hours. Next, 100 parts of 50% -NaOH was added, and hydrolysis was performed at 90 ° C. for 1 hour.
【００３０】得られた粉末をＮＭＲで分析したところ、
カルボキシル変性率は２９．３モル％であった。When the obtained powder was analyzed by NMR,
The carboxyl modification rate was 29.3 mol%.
【００３１】製造例２ ５０％−アクリルアミド水溶液４８４部の代わりに、ア
クリロニトリル２５０部を用いた以外は、すべて製造例
１と同様の操作を行った。得られた粉末をＮＭＲで分析
したところ、カルボキシル変性率は３７．６モル％であ
った。 Production Example 2 The same operation as in Production Example 1 was carried out except that 250 parts of acrylonitrile were used instead of 484 parts of a 50% aqueous acrylamide solution. When the obtained powder was analyzed by NMR, the carboxyl modification rate was 37.6 mol%.
【００３２】製造例３ ４リットル容の横形ブレンダーにＰＶＡ（重合度１，７
００、けん化度９８．５モル％）４４０部、５０％−Ｎ
ａＯＨ水溶液２８０部、及び５０％−ＡＭＰＳ水溶液８
２８部を加え、８０℃で７時間攪拌した。得られた粉末
をＮＭＲで分析したところ、スルホン基変性率は１４．
３モル％であった。 Production Example 3 PVA (degree of polymerization 1,7) was placed in a 4-liter horizontal blender.
00, degree of saponification 98.5 mol%) 440 parts, 50% -N
280 parts of aOH aqueous solution and 50% -AMPS aqueous solution 8
28 parts were added and stirred at 80 ° C. for 7 hours. When the obtained powder was analyzed by NMR, the sulfone group modification rate was 14.
3 mol%.
【００３３】製造例４ ４リットル容の横形ブレンダーにＰＶＡ（重合度５，０
００、けん化度９８．２モル％）４４０部、３０％−Ｎ
ａＯＨ水溶液７０部、及び５０％−アクリルアミド水溶
液２８４部を加え、６０℃で４時間攪拌した。次いで５
０％−ＮａＯＨ１２５部を加え、７０℃で１時間加水分
解を行った。 Production Example 4 PVA (polymerization degree 5,0) was added to a 4-liter horizontal blender.
00, saponification degree 98.2 mol%) 440 parts, 30% -N
70 parts of an aOH aqueous solution and 284 parts of a 50% -acrylamide aqueous solution were added, followed by stirring at 60 ° C. for 4 hours. Then 5
125 parts of 0% -NaOH was added, and the mixture was hydrolyzed at 70 ° C. for 1 hour.
【００３４】次いで、５０％−ＡＭＰＳナトリウム塩水
溶液４６０部を加え、８０℃で４時間攪拌した。得られ
た粉末をＮＭＲで分析したところ、カルボキシル変性率
は１７．３モル％、スルホン基変性率は６．５モル％で
あった。Next, 460 parts of a 50% -AMPS sodium salt aqueous solution was added, and the mixture was stirred at 80 ° C. for 4 hours. When the obtained powder was analyzed by NMR, the carboxyl modification rate was 17.3 mol% and the sulfone group modification rate was 6.5 mol%.
【００３５】製造例５ ４リットル容の横形ブレンダーにＰＶＡ（重合度１，６
００、けん化度９９．２モル％）４４０部、３０％−Ｎ
ａＯＨ水溶液７部、及び５０％−アクリルアミド水溶液
２８部を加え、６０℃で２時間攪拌した。次いで５０％
−ＮａＯＨ１２部を加え、７０℃で１時間加水分解を行
った。 Production Example 5 PVA (degree of polymerization 1,6) was placed in a 4 liter horizontal blender.
00, degree of saponification 99.2 mol%) 440 parts, 30% -N
7 parts of an aOH aqueous solution and 28 parts of a 50% -acrylamide aqueous solution were added, and the mixture was stirred at 60 ° C for 2 hours. Then 50%
-12 parts of NaOH was added, and hydrolysis was performed at 70 ° C for 1 hour.
【００３６】得られた粉末をＮＭＲで分析したところ、
カルボキシル変性率は１．６モル％であった。When the obtained powder was analyzed by NMR,
The carboxyl modification rate was 1.6 mol%.
【００３７】製造例６ ４リットル容の横形ブレンダーにＰＶＡ（重合度５０
０、けん化度９８．８モル％）４４０部、３０％−Ｎａ
ＯＨ水溶液２００部、及び５０％−アクリルアミド水溶
液４５０部を加え、６０℃で８時間攪拌した。次いで５
０％−ＮａＯＨ１００部を加え、９０℃で１時間加水分
解を行った。 Production Example 6 PVA (degree of polymerization: 50) was placed in a 4-liter horizontal blender.
0, saponification degree 98.8 mol%) 440 parts, 30% -Na
200 parts of an OH aqueous solution and 450 parts of a 50% -acrylamide aqueous solution were added, followed by stirring at 60 ° C. for 8 hours. Then 5
100 parts of 0% -NaOH was added, and the mixture was hydrolyzed at 90 ° C. for 1 hour.
【００３８】得られた粉末をＮＭＲで分析したところ、
カルボキシル変性率は２５．３モル％であった。When the obtained powder was analyzed by NMR,
The carboxyl modification rate was 25.3 mol%.
【００３９】製造例７ ４リットル容の横形ブレンダーにＰＶＡ（重合度２５０
０、けん化度９８．８モル％）４４０部、２５％−Ｎａ
ＯＨ水溶液３０部、及び５０％−アクリルアミド水溶液
４２６部を加え、３０℃で７時間攪拌した。 Production Example 7 PVA (degree of polymerization 250) was placed in a 4-liter horizontal blender.
0, saponification degree 98.8 mol%) 440 parts, 25% -Na
30 parts of an OH aqueous solution and 426 parts of a 50% -acrylamide aqueous solution were added, and the mixture was stirred at 30 ° C for 7 hours.
【００４０】得られた粉末をＮＭＲで分析したところ、
アミド基変性率は２６．１モル％であった。When the obtained powder was analyzed by NMR,
The amide group modification rate was 26.1 mol%.
【００４１】製造例８ ４リットル容の横形ブレンダーにＰＶＡ（重合度２，５
００、けん化度９８．８モル％）４４０部、２５％−Ｎ
ａＯＨ水溶液７７部、及び５０％−アクリルアミド水溶
液４２６部を加え、３０℃で４時間攪拌した。次いで、
４８％ＮａＯＨ水溶液８３部を加え、７０℃で１時間攪
拌した。 Production Example 8 PVA (degree of polymerization 2.5, 5) was placed in a 4-liter horizontal blender.
00, saponification degree 98.8 mol%) 440 parts, 25% -N
An aOH aqueous solution (77 parts) and a 50% -acrylamide aqueous solution (426 parts) were added, and the mixture was stirred at 30 ° C for 4 hours. Then
83 parts of a 48% NaOH aqueous solution was added, and the mixture was stirred at 70 ° C for 1 hour.
【００４２】得られた粉末をＮＭＲで分析したところ、
アミド基変性率は１２．１モル％、カルボキシル変性率
は１３．３モル％であった。When the obtained powder was analyzed by NMR,
The amide group modification rate was 12.1 mol%, and the carboxyl modification rate was 13.3 mol%.
【００４３】製造例９ 酢酸ビニル７５部、メタノール５００部、イタコン
酸４．８５部、ＮａＯＨ１．ｌ０部、アゾビスイソブチ
ロニトリル０．３部をセバラブルフラスコに仕込み、７
０℃で９時間重合した。この時の重合率は８１％であっ
た。未反応の酢酸ビニルを除去したのち、理論量の１／
１０のＮａＯＨを加え、４０℃で５時間けん化した。得
られたカルボキシ変性ＰＶＡの重合度は１，２００、け
ん化度は９６．３モル％であった。また、ＮＭＲで分析
したところ、カルボキシル変性率は３．３モル％であっ
た。 Production Example 9 75 parts of vinyl acetate, 500 parts of methanol, 4.85 parts of itaconic acid, 1 part of NaOH. 10 parts and 0.3 parts of azobisisobutyronitrile were charged into a separable flask, and
Polymerization was carried out at 0 ° C. for 9 hours. At this time, the polymerization rate was 81%. After removing unreacted vinyl acetate, 1 / theoretical amount
10 NaOH was added and saponified at 40 ° C. for 5 hours. The degree of polymerization of the obtained carboxy-modified PVA was 1,200, and the degree of saponification was 96.3 mol%. In addition, as analyzed by NMR, the carboxyl modification rate was 3.3 mol%.
【００４４】 で得られたカルボキシル変性ＰＶＡ
４００部に、３０％ＮａＯＨ水溶液１８０部、及び５０
％−アクリルアミド水溶液４００部を加え、６０℃で８
時間攪拌した。次いで５０％ＮａＯＨ８０部を加え、９
０℃で１時間加水分解した。The carboxyl-modified PVA obtained in
To 400 parts, 180 parts of a 30% NaOH aqueous solution, and 50 parts
% -Acrylamide aqueous solution (400 parts),
Stirred for hours. Next, 80 parts of 50% NaOH was added, and
Hydrolyzed at 0 ° C. for 1 hour.
【００４５】得られた粉末をＮＭＲで分析したところ、
カルボキシル変性率は２５％であった。When the obtained powder was analyzed by NMR,
The carboxyl modification rate was 25%.
【００４６】実施例１〜１８、比較例１〜２０ 表１に示した農薬粒剤配合処方に従って農薬粒剤組成物
を調製し、水を加えて混練した後、押し出し式造粒機で
粒化して農薬粒剤を得た。崩壊剤としては表２に示した
もの、粘結剤としては表３に示したものを用いた。 Examples 1 to 18 and Comparative Examples 1 to 20 A pesticide granule composition was prepared according to the pesticide granule formulation shown in Table 1, kneaded with water, and granulated by an extrusion granulator. To obtain pesticide granules. The disintegrants shown in Table 2 were used, and the binders shown in Table 3 were used.
【００４７】[0047]
【表１】 。[Table 1] .
【００４８】[0048]
【表２】 。[Table 2] .
【００４９】[0049]
【表３】 。[Table 3] .
【００５０】上記により得られた農薬粒剤の風乾後の硬
度、水中崩壊性を以下の方法により調べた。結果を表４
に示す。The hardness of the pesticide granules obtained above after drying in air and the disintegration property in water were examined by the following methods. Table 4 shows the results
Shown in
【００５１】粒剤の硬度測定試験 上記により得られた粒剤を３２メッシュでふるい、ふる
った粒剤１００ｇを精秤し、内径１００ｍｍ×内深１０
０ｍｍ×外径１２０ｍｍの円筒容器に磁製玉３個（計１
０５ｇ）と共に入れ、蓋をした。 Granule hardness measurement test The granules obtained above were sieved with a 32 mesh, 100 g of the sieved granules were precisely weighed, and the inner diameter was 100 mm and the inner depth was 10 mm.
Three porcelain balls (1 in total) in a cylindrical container of 0 mm x 120 mm outer diameter
05g) and capped.
【００５２】この円筒容器を、回転数７５回／分で回転
するローラー上に置き、１５分後に内容物を取り出して
３２メッシュでふるい、残った粒剤の重量（Ｗ）を正確
に量った。The cylindrical container was placed on a roller rotating at a rotation speed of 75 times / minute. After 15 minutes, the contents were taken out and sieved with 32 mesh, and the weight (W) of the remaining granules was measured accurately. .
【００５３】次式により崩壊率（％）を求めた。The decay rate (%) was determined by the following equation.
【００５４】[0054]
【式１】 。(Equation 1) .
【００５５】粒剤の水中崩壊性試験 直径２５ｃｍ、深さ４ｃｍのシャーレに標準硬水（５
°）を深さ１ｃｍになるように注入した。次いで両切り
ガラス管をシャーレの中心に立て、粒剤０．５ｇをガラ
ス管に入れた。 Underwater Disintegration Test of Granules A standard hard water (5 cm) was placed in a Petri dish 25 cm in diameter and 4 cm in depth.
°) was injected to a depth of 1 cm. Next, the both-cut glass tubes were set up at the center of the Petri dish, and 0.5 g of the granules were put in the glass tubes.
【００５６】ガラス管を静かに引き上げ、粒剤の崩壊性
を測定した。崩壊性は崩壊した粒剤が拡散した幅（ｃ
ｍ）の最短値及び最長値を５分、１０分、３０分後に測
定し、その平均を示した。The glass tube was gently pulled up, and the disintegration of the granules was measured. The disintegration is determined by the width (c)
The shortest value and the longest value of m) were measured after 5, 10 and 30 minutes, and the average was shown.
【００５７】総合評価 上記のようにして調べた硬度および水中崩壊性から、下
記の基準で粒剤の総合評価を行った。結果を表４に併せ
て示す。 Comprehensive Evaluation The granules were comprehensively evaluated on the basis of the following criteria from the hardness and disintegration property in water determined as described above. The results are shown in Table 4.
【００５８】◎：粒剤の硬度および水中崩壊性が極めて
優れている。A: The hardness of the granules and the disintegration in water are extremely excellent.
【００５９】○：粒剤の硬度および水中崩壊性が良好で
ある。：: Good hardness and disintegration in water of the granules.
【００６０】×：粒剤の硬度および水中崩壊性が極めて
劣る。X: The hardness and disintegration in water of the granules are extremely poor.
【００６１】[0061]
【表４】 。[Table 4] .
【００６２】[0062]
【発明の効果】請求項１〜３の本発明の農薬粒剤組成物
は、ノニオンまたはアニオン基変性ＰＶＡを必須成分と
することから、 １．バインダー力が強い、 ２．水溶性であるため、水中崩壊分散性が良好である、 等の特長を有している。The pesticidal granule composition of the present invention according to claims 1 to 3 comprises nonionic or anionic group-modified PVA as an essential component. 1. Strong binder power Since it is water-soluble, it has characteristics such as good disintegration and dispersibility in water.
【００６３】従って、本発明の農薬粒剤組成物によれ
ば、輸送時や保管時には崩壊せず、水中に投入した時に
は速やかに崩壊拡散し、農薬効果を最大限に発揮する農
薬粒剤が得られる。Therefore, according to the pesticide granule composition of the present invention, the pesticide granule which does not disintegrate during transportation or storage, rapidly disintegrates and diffuses when put into water, and exhibits the pesticide effect to the maximum can be obtained. Can be
Claims (3)
上のビニル化合物をマイケル付加して得られる、あるい
はマイケル付加したのち一部又は完全に加水分解して得
られる、ノニオン変性及び／又はアニオン変性ポリビニ
ルアルコールを配合してなる農薬粒剤組成物。1. A nonion-modified and / or anion-modified polyvinyl obtained by Michael addition of one or more vinyl compounds to polyvinyl alcohol, or partially or completely hydrolyzed after Michael addition. A pesticide granule composition containing alcohol.
ポリビニルアルコールが、ポリビニルアルコールにアク
リロニトリル又はアクリルアミドをマイケル付加して得
られる、あるいはマイケル付加したのち一部又は完全に
加水分解して得られる変性ポリビニルアルコールである
ことを特徴とする、請求項１に記載の農薬粒剤組成物。2. The modified nonionic and / or anionic modified polyvinyl alcohol obtained by Michael addition of acrylonitrile or acrylamide to polyvinyl alcohol, or modified polyvinyl alcohol obtained by Michael addition followed by partial or complete hydrolysis. The pesticide granule composition according to claim 1, wherein:
ポリビニルアルコールが、ポリビニルアルコール又は請
求項２の変性ポリビニルアルコールに２−アクリルアミ
ド−２−メチルプロパン−３−スルホン酸あるいはその
塩をマイケル付加して得られる変性ポリビニルアルコー
ルであることを特徴とする、請求項１に記載の農薬粒剤
組成物。3. The nonionic-modified and / or anion-modified polyvinyl alcohol is obtained by Michael addition of 2-acrylamido-2-methylpropane-3-sulfonic acid or a salt thereof to polyvinyl alcohol or the modified polyvinyl alcohol of claim 2. The pesticidal granule composition according to claim 1, which is a modified polyvinyl alcohol to be obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15109496A JPH101403A (en) | 1996-06-12 | 1996-06-12 | Agrochemical granular agent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15109496A JPH101403A (en) | 1996-06-12 | 1996-06-12 | Agrochemical granular agent composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH101403A true JPH101403A (en) | 1998-01-06 |
Family
ID=15511211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15109496A Pending JPH101403A (en) | 1996-06-12 | 1996-06-12 | Agrochemical granular agent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH101403A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017038946A1 (en) * | 2015-09-04 | 2017-03-09 | 住友化学株式会社 | Composition, method for producing composition, and pesticide composition |
-
1996
- 1996-06-12 JP JP15109496A patent/JPH101403A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017038946A1 (en) * | 2015-09-04 | 2017-03-09 | 住友化学株式会社 | Composition, method for producing composition, and pesticide composition |
| CN107920528A (en) * | 2015-09-04 | 2018-04-17 | 住友化学株式会社 | Composition, the manufacture method of composition and composition pesticide |
| AU2016317605B2 (en) * | 2015-09-04 | 2021-01-07 | Sumitomo Chemical Company, Limited | Composition, method for producing composition, and pesticide composition |
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