JPH045258A - Stabilization of alkylene glycol monosorbate - Google Patents
Stabilization of alkylene glycol monosorbateInfo
- Publication number
- JPH045258A JPH045258A JP10826690A JP10826690A JPH045258A JP H045258 A JPH045258 A JP H045258A JP 10826690 A JP10826690 A JP 10826690A JP 10826690 A JP10826690 A JP 10826690A JP H045258 A JPH045258 A JP H045258A
- Authority
- JP
- Japan
- Prior art keywords
- phosphite
- alkylene glycol
- sorbate
- glycol monosorbate
- monosorbate
- 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.)
- Granted
Links
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- -1 alkylene glycol Chemical compound 0.000 title claims abstract description 31
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 230000006641 stabilisation Effects 0.000 title description 3
- 238000011105 stabilization Methods 0.000 title description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 16
- WJJPRLNGARPWEW-WJPDYIDTSA-N C\C=C\C=C\C(=O)OCCCO Chemical compound C\C=C\C=C\C(=O)OCCCO WJJPRLNGARPWEW-WJPDYIDTSA-N 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims abstract description 6
- BJLLGOQTEAOBJJ-MQQKCMAXSA-N 2-hydroxyethyl (2e,4e)-hexa-2,4-dienoate Chemical compound C\C=C\C=C\C(=O)OCCO BJLLGOQTEAOBJJ-MQQKCMAXSA-N 0.000 claims abstract description 3
- ZGRJLKBNVVUHIY-AOGGBPEJSA-N C\C=C\C=C\C(=O)OCCCCO Chemical compound C\C=C\C=C\C(=O)OCCCCO ZGRJLKBNVVUHIY-AOGGBPEJSA-N 0.000 claims abstract 2
- WYPOCAVDDXABIF-UHFFFAOYSA-N didecyl hydrogen phosphite Chemical compound CCCCCCCCCCOP(O)OCCCCCCCCCC WYPOCAVDDXABIF-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 13
- 230000000087 stabilizing effect Effects 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 2
- 239000003429 antifungal agent Substances 0.000 abstract 1
- 230000002070 germicidal effect Effects 0.000 abstract 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229940075582 sorbic acid Drugs 0.000 description 2
- 235000010199 sorbic acid Nutrition 0.000 description 2
- 239000004334 sorbic acid Substances 0.000 description 2
- LERHZMJSGTXXMF-RJNTXXOISA-L (2e,4e)-hexa-2,4-dienoate;iron(2+) Chemical compound [Fe+2].C\C=C\C=C\C([O-])=O.C\C=C\C=C\C([O-])=O LERHZMJSGTXXMF-RJNTXXOISA-L 0.000 description 1
- GRTWTVFDPBKQNU-MQQKCMAXSA-N (2e,4e)-hexa-2,4-dienoyl chloride Chemical compound C\C=C\C=C\C(Cl)=O GRTWTVFDPBKQNU-MQQKCMAXSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- SCVZKPKDMFXESQ-VSAQMIDASA-N butyl (2e,4e)-hexa-2,4-dienoate Chemical compound CCCCOC(=O)\C=C\C=C\C SCVZKPKDMFXESQ-VSAQMIDASA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229960003505 mequinol Drugs 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、アルキレングリコールモノソルベートの安定
化方法に関する。更に詳しくはアルキレングリコールモ
ノソルベートニ亜リン酸エステルを添加することによる
アルキレングリコールモノソルベートの安定化方法に関
する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for stabilizing alkylene glycol monosorbate. More specifically, the present invention relates to a method for stabilizing alkylene glycol monosorbate by adding an alkylene glycol monosorbate diphosphite.
一般式ＣＩ）
ＨＨ１１
（式中のＣｎＨｍは炭素数２〜４のアルキレン基を表わ
す。）
で表わされるアルキレングリコールモノベートは、防カ
ビ剤、防菌剤として使用されている（ヨーロビアンジャ
ーナルオブメデシナルケミストリーキミカテラペエテイ
ク（Ｅｕｒｏｐｅａｎ Ｊｏｕｒｈａｌ ｏｆＭｅｄｉ
ｃｉｎａｌ Ｃｈｅｍｉｓｔｒｙ Ｃｈｉｍｉｃａ Ｔ
ｈｅｒａｐｅｔｉｌｕｅ）１８ ｐ４４１〜４４５ （
１９８３） ）。The alkylene glycol monobate represented by the general formula CI) HH11 (CnHm in the formula represents an alkylene group having 2 to 4 carbon atoms) is used as a fungicide and a bactericidal agent (European Journal of Medicine). European Jourhal of Medi
cinal Chemistry Chimica T
herapetilue) 18 p441-445 (
1983) ).
また、磁気コーティング剤（４Ｉ開昭５８−２１３０６
５号）として使用されるなど種々の用途で使用されてい
る。In addition, magnetic coating agent (4I Kaisho 58-21306
It is used for various purposes such as No. 5).
（従来の技術）
上述の如き用途に有用なアルキレングリコールモノソル
ベートの有効な安定化方法は低温下に保存する以外知ら
れていない。(Prior Art) There is no known effective method for stabilizing alkylene glycol monosorbates useful for the above-mentioned uses other than storing them at low temperatures.
（発明が解決しようとする課題）
一般式ＣＩ）で表わされるアルキレングリコールモノソ
ルベートは、その高度に不飽和な構造に起因して、不安
定な物質であって室温以上での長期の貯蔵においては、
重合、ゲル化を起こしゃすく使用が困難となるといった
問題点を有している。(Problems to be Solved by the Invention) Alkylene glycol monosorbate represented by the general formula CI) is an unstable substance due to its highly unsaturated structure, and cannot be stored for long periods at room temperature or higher. teeth,
It has the problem that it tends to polymerize and gel, making it difficult to use.
貯蔵時における重合、ゲル化による変質は、製品の品位
を害して商品価値を低下させることとなる。この場合貯
蔵時において重合防止をするため安定化剤等の添加を必
要とするが、今までのところ有効な安定化剤は見い出さ
れておらず、有効な安定化方法が切望されているのが現
状である。Deterioration due to polymerization and gelation during storage impairs the quality of the product and reduces its commercial value. In this case, it is necessary to add a stabilizer to prevent polymerization during storage, but no effective stabilizer has been found so far, and an effective stabilization method is desperately needed. This is the current situation.
本発明者らは、アルキレングリコールモノソルベートの
安定化方法について鋭意研究した。その結果、アルキレ
ングリフールモノソルベートニ亜リン酸エステルを添加
することによシ該アルキレングリコールモノソルベート
が長期に安定化されることを見い出し、この知見にもと
づき本発明を完成した。以上の記述から明らかなように
本発明の目的はアルキレングリコールモノソルベートの
安定化方法を提供することである。The present inventors have conducted intensive research on methods for stabilizing alkylene glycol monosorbate. As a result, it was discovered that the alkylene glycol monosorbate was stabilized for a long period of time by adding alkylene glycol monosorbate diphosphite, and based on this knowledge, the present invention was completed. As is clear from the above description, an object of the present invention is to provide a method for stabilizing alkylene glycol monosorbate.
（課題を解決するための手段）
本発明は、一般式ＣＩ］
（式中、ＣｎＨｍは炭素数２〜４のアルキレン基を表わ
す。）
で表わされるアルキレングリコールモノソルベートに亜
リン酸エステルを添加することを特徴とするアルキレン
グリコールモノソルベートの安定化方法である。本発明
でいう上記一般式ＣＩ）の構造を有するアルキレングリ
コールモノソルベートは、例えばヒドロキシエチルソル
ベー）（ｎ＝２、ｍ＝４ ）、ヒドロキシプロピルソル
ベー） （ｎ＝３、ｍ＝７）、ヒドロキシブチルソルベ
ート（ｎ＝４、ｍ＝９）をあげることができる。(Means for Solving the Problems) The present invention provides a solution in which a phosphite is added to an alkylene glycol monosorbate represented by the general formula CI] (wherein, CnHm represents an alkylene group having 2 to 4 carbon atoms). This is a method for stabilizing alkylene glycol monosorbate, which is characterized by: In the present invention, the alkylene glycol monosorbates having the structure of the above general formula CI) include, for example, hydroxyethyl sorbate (n=2, m=4), hydroxypropyl sorbate) (n=3, m=7), hydroxypropyl sorbate) (n=3, m=7), Butyl sorbate (n=4, m=9) can be mentioned.
一般式ＣＩ〕で表わされるアルキレングリコールモノソ
ルベートは、例えば有機塩基の存在下ソルビン酸クロラ
イドとアルキレングリコール（ｌ、２−エタンジオール
、１．２−フロパンジオール、１゜２−ブタンジオール
）と反応させる方法、ソルビン酸と酸化アルキレン（エ
チレンオキサイド、プロピレンオキサイド、ブチレンオ
キサイド）を反応させる方法によシ製造され、次いで精
製工程を経て得られる。The alkylene glycol monosorbate represented by the general formula CI] can be prepared, for example, by combining sorbic acid chloride and alkylene glycol (1,2-ethanediol, 1,2-furopanediol, 1.2-butanediol) in the presence of an organic base. It is produced by a method of reacting sorbic acid with alkylene oxide (ethylene oxide, propylene oxide, butylene oxide), and then a purification process.
本発明において使用する亜リン酸エステルは、トリフェ
ニルホスファイト、ジデシルモノフェニルホスファイト
、トリスノニルフェニルホスファイトであシ、一般式［
Ｉ）の化合物に亜リン酸エステルを添加することによシ
、効果的にアルキレンモノツルベートの重合、ゲル化を
防止でき、アルキレングリコールモノソルベートの安定
化が達成される。The phosphite used in the present invention is triphenyl phosphite, didecylmonophenyl phosphite, trisnonylphenyl phosphite, and has the general formula [
By adding a phosphite to the compound I), polymerization and gelation of alkylene monoturbate can be effectively prevented, and stabilization of alkylene glycol monosorbate can be achieved.
該亜リン酸エステルは、アルキレングリコールモノソル
ベートに添加する際、よく分散溶解させることが必要で
、機械的な撹拌もしくは不活性ガスを使用したバブリン
グを行なうことが望ましい。When the phosphite is added to the alkylene glycol monosorbate, it is necessary to disperse and dissolve it well, and it is preferable to perform mechanical stirring or bubbling using an inert gas.
亜リン酸エステルの使用量は、特に限定されないがアル
キレングリコールに対して０．００１重量係〜５重量係
が好ましく、よシ好ましくはｏ、ｏｏｓ重量％〜１．０
重量係である。０．００１重量％よシ少ない場合は、安
定化効果が小さく、また、５重量釜以上では、経済的理
由で有利で危い。The amount of phosphite used is not particularly limited, but it is preferably 0.001 to 5 weight percent relative to the alkylene glycol, and more preferably o, oos weight percent to 1.0 weight percent.
He is in charge of weight. If the amount is less than 0.001% by weight, the stabilizing effect will be small, and if it is more than 5 weight percent, it is not advantageous or dangerous for economic reasons.
また本発明においては、他の酸化防止剤、例えば２，６
−シーｔｅｒｔ−ブチル−ｐ−クレゾールやハイドロキ
ノン七ツメチルエーテルを併用しても差支えなく、安定
化効果を妨げずに好結果が得られる。In addition, in the present invention, other antioxidants, such as 2,6
-tert-butyl-p-cresol or hydroquinone methyl ether may be used in combination, and good results can be obtained without interfering with the stabilizing effect.
（実施例）
以下実施例にもとすき本発明を具体的に説明するが、本
発明は、これによって限定されるものではない。(Example) The present invention will be specifically explained in Examples below, but the present invention is not limited thereto.
実施例１〜７
トルエン中ソルビン酸と酸化プロピレンとをソルビン酸
鉄を触媒として反応させてヒドロキシプロピルソルベー
トを合成した。この反応液を炭酸ナトリウム水溶液で洗
浄して、触媒を除去して粗ヒドロキシプロピルソルベー
トを調製した。この粗精製液を真空下でトルエン留分を
前留分としてカットしたのち、５ｗＨｇ真空下１２０〜
１３５℃のヒドロキシプロピルソルベート画分を得て蒸
留精製した。Examples 1 to 7 Hydroxypropyl sorbate was synthesized by reacting sorbic acid and propylene oxide in toluene using iron sorbate as a catalyst. This reaction solution was washed with an aqueous sodium carbonate solution to remove the catalyst and prepare crude hydroxypropyl sorbate. This crude purified liquid was cut under vacuum with the toluene fraction as a pre-distillate, and then
A hydroxypropyl sorbate fraction at 135°C was obtained and purified by distillation.
蒸留したヒドロキシプロピルソルベートノカスクロ純度
は９９．５重量係で残シ０．３重量釜がジプロピレンク
リコールモノツルベート、α２１ｉ量％がプロピレング
リコールジソルベートであった。The purity of the distilled hydroxypropyl sorbate was 99.5% by weight, with the remaining 0.3% by weight being dipropylene glycol monoturbate and α21% by weight being propylene glycol disolbate.
また得られたヒドロキシプロピルソルベートノ酸価は０
． Ｑ ３１１１１ｐ ＫＯＨ，＃、水酸価は３３１．
０ ＭＰＫＯＨ／１！であった。このようにして得たヒ
ドロキシプロピルソルベート各１００ｇに安定化剤とし
て後述の第１表に記載の亜リン酸エステルを同表に記載
の割合で添加してよく撹拌したのち、４０℃±３℃に保
れた保温６中に入れて経時的に試料を取り出しその試料
の粘度をＥ型粘度計を用いて温度２５℃で測定して安定
性を評価した。In addition, the obtained hydroxypropyl sorbate acid value was 0.
．． Q 31111p KOH, #, hydroxyl value is 331.
0 MPKOH/1! Met. To each 100 g of the hydroxypropyl sorbate obtained in this manner, a phosphite ester listed in Table 1 below was added as a stabilizer in the proportions listed in the same table, and after stirring well, the mixture was heated to 40°C ± 3°C. The sample was placed in a heat insulating chamber 6 kept at a temperature of 25° C., and the sample was taken out over time, and the viscosity of the sample was measured using an E-type viscometer at a temperature of 25° C. to evaluate stability.
また比較例Ｌ２として実施例１〜７に用いたのと同様の
ヒドロキシプロピルソルベー）各１００Ｉに比較例１は
、安定化剤を添加せず、比較例２は、２，６−ジーｔ−
ブチル−４−メチルフェノール０．０４重重量を添加し
て実施例１〜７に準じて保存し、粘度の経時的変化を測
定して安定性を評価した。In addition, as Comparative Example L2, the same hydroxypropyl solvate as that used in Examples 1 to 7) was added to each 100I. In Comparative Example 1, no stabilizer was added, and in Comparative Example 2, 2,6-di-t-
0.04 weight of butyl-4-methylphenol was added and stored according to Examples 1 to 7, and stability was evaluated by measuring changes in viscosity over time.
実施各側、比較各側の結果を第１表にまとめて示した。The results of each implementation side and each comparison side are summarized in Table 1.
（発明の効果）
従来までアルキレングリコールモノソルベートは、低温
下で保存しなければならなかったが、本発明の方法を使
用することにより、アルキレングリコールモノソルベー
トを長期にわたって室温で安定的に貯蔵、保存すること
が可能である。(Effect of the invention) Conventionally, alkylene glycol monosorbate had to be stored at low temperature, but by using the method of the present invention, alkylene glycol monosorbate can be stored stably at room temperature for a long period of time. , it is possible to save.
以上that's all
Claims (4)
コールモノソルベートに亜リン酸エステルを添加するこ
とを特徴とするアルキレングリコールモノソルベートの
安定化方法。 ▲数式、化学式、表等があります▼〔 I 〕 （式中、ＣｎＨｍは炭素数２〜４のアルキレン基を表わ
す。）(1) A method for stabilizing alkylene glycol monosorbate, which comprises adding a phosphite to alkylene glycol monosorbate represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, CnHm represents an alkylene group having 2 to 4 carbon atoms.)
ートに亜リン酸エステル０．００５〜５重量％を添加す
ることを特徴とするアルキレングリコールモノソルベー
トの安定化方法。(2) A method for stabilizing alkylene glycol monosorbate, which comprises adding 0.005 to 5% by weight of phosphite to the alkylene glycol monosorbate according to claim 1.
シエチルソルベート、ヒドロキシプロピルソルベート、
ヒドロキシブチルソルベートもしくはこれらの２種以上
の混合物である請求項１もしくは請求項２のいずれか１
項のアルキレングリコールモノソルベートの安定化方法
。(3) Alkylene glycol monosorbate is hydroxyethyl sorbate, hydroxypropyl sorbate,
Either claim 1 or claim 2, which is hydroxybutyl sorbate or a mixture of two or more thereof.
Method for stabilizing alkylene glycol monosorbate in Section.
ジデシルモノホスファイト、トリスノニルフェニルホス
ファイトもしくはこれらの２種以上の混合物である請求
項１もしくは請求項２のいずれか１項記載のアルキレン
グリコールモノソルベートの安定化方法。(4) Phosphite is triphenyl phosphite,
The method for stabilizing alkylene glycol monosorbate according to claim 1 or 2, wherein the stabilizer is didecyl monophosphite, trisnonylphenyl phosphite, or a mixture of two or more thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10826690A JP2814291B2 (en) | 1990-04-24 | 1990-04-24 | Method for stabilizing alkylene glycol monosorbate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10826690A JP2814291B2 (en) | 1990-04-24 | 1990-04-24 | Method for stabilizing alkylene glycol monosorbate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH045258A true JPH045258A (en) | 1992-01-09 |
| JP2814291B2 JP2814291B2 (en) | 1998-10-22 |
Family
ID=14480292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10826690A Expired - Lifetime JP2814291B2 (en) | 1990-04-24 | 1990-04-24 | Method for stabilizing alkylene glycol monosorbate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2814291B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0635209A1 (en) * | 1993-02-08 | 1995-01-25 | Asahi Denka Kogyo Kabushiki Kaisha | Aquatic pest control drug |
-
1990
- 1990-04-24 JP JP10826690A patent/JP2814291B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0635209A1 (en) * | 1993-02-08 | 1995-01-25 | Asahi Denka Kogyo Kabushiki Kaisha | Aquatic pest control drug |
| EP0635209B1 (en) * | 1993-02-08 | 2000-05-17 | Asahi Denka Kogyo Kabushiki Kaisha | Aquatic pest control drug |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2814291B2 (en) | 1998-10-22 |
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