JPH10310570A - Aqueous solution of calcium ethylenebis(thiocarbamate) having low-temperature crystallization stability - Google Patents
Aqueous solution of calcium ethylenebis(thiocarbamate) having low-temperature crystallization stabilityInfo
- Publication number
- JPH10310570A JPH10310570A JP15422397A JP15422397A JPH10310570A JP H10310570 A JPH10310570 A JP H10310570A JP 15422397 A JP15422397 A JP 15422397A JP 15422397 A JP15422397 A JP 15422397A JP H10310570 A JPH10310570 A JP H10310570A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- calcium
- ethylenebis
- dithiocarbamate
- ethylenebisdithiocarbamate
- 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
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 24
- 238000002425 crystallisation Methods 0.000 title claims abstract description 6
- 230000008025 crystallization Effects 0.000 title claims abstract description 6
- HOLMLIJCTACYMK-UHFFFAOYSA-L calcium N-[2-(sulfidocarbonylamino)ethyl]carbamothioate Chemical compound C(CNC([O-])=S)NC([O-])=S.[Ca+2] HOLMLIJCTACYMK-UHFFFAOYSA-L 0.000 title 1
- YRGVIQAQIXMJIO-UHFFFAOYSA-L calcium;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Ca+2].[S-]C(=S)NCCNC([S-])=S YRGVIQAQIXMJIO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 abstract description 5
- UQJQVUOTMVCFHX-UHFFFAOYSA-L nabam Chemical compound [Na+].[Na+].[S-]C(=S)NCCNC([S-])=S UQJQVUOTMVCFHX-UHFFFAOYSA-L 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 230000000638 stimulation Effects 0.000 abstract description 2
- 239000012990 dithiocarbamate Substances 0.000 description 8
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 6
- QRNATDQRFAUDKF-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate Chemical compound NC(=S)SCCSC(N)=S QRNATDQRFAUDKF-UHFFFAOYSA-N 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000004781 supercooling Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000012991 xanthate Substances 0.000 description 2
- VAFJOEUOKVHNIQ-UHFFFAOYSA-N C(N)(SCCSC(N)=S)=S.[Ca] Chemical compound C(N)(SCCSC(N)=S)=S.[Ca] VAFJOEUOKVHNIQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- KLQDQAPDIQDTFT-UHFFFAOYSA-L disodium ethene dicarbamodithioate Chemical compound C(N)([S-])=S.C=C.[Na+].[Na+].C(N)([S-])=S KLQDQAPDIQDTFT-UHFFFAOYSA-L 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】エチレンビスジチオカルバミン酸
カルシウム塩を３０〜５０重量％含有し、０℃以下の低
温でも晶析安定性を有するエチレンビスジチオカルバミ
ン酸カルシウム塩水溶液に関する。The present invention relates to an aqueous solution of calcium ethylenebisdithiocarbamate containing 30 to 50% by weight of calcium ethylenebisdithiocarbamate and having crystallization stability even at a low temperature of 0 ° C. or lower.
【０００２】[0002]
【従来の技術】ジチオカルバミン酸塩は、従来からゴム
用加硫促進剤、農園芸用殺菌剤、防カビ剤、金属表面処
理剤、飛灰処理剤及び潤滑油の極圧添加剤等に使用され
ている。2. Description of the Related Art Dithiocarbamates are conventionally used as vulcanization accelerators for rubber, fungicides for agricultural and horticultural use, fungicides, metal surface treatment agents, fly ash treatment agents and extreme pressure additives for lubricating oils. ing.
【０００３】ジチオカルバミン酸塩の１種であるエチレ
ンビスジチオカルバミン酸カルシウム塩の水溶液は、農
園芸用殺菌剤であるとともに、植物の重要な栄養素の１
つであるカルシウムを含有していることから植物活性剤
としても需要が見込まれ、更にスライムコントロール剤
としても大いに見込まれている。これらの需要に対して
輸送や貯蔵等の経済上の理由から濃厚溶液とされるのが
一般的である。ところが最近、特に寒冷地での低温にお
いても晶析しない安定な濃厚溶液が該業界から強く求め
られている。An aqueous solution of calcium ethylenebisdithiocarbamate, a kind of dithiocarbamate, is an agricultural and horticultural fungicide and one of the important nutrients of plants.
Since it contains calcium, it is expected to be used as a plant active agent, and is also expected to be used as a slime control agent. To meet these demands, it is common to use concentrated solutions for economic reasons such as transportation and storage. However, recently, there has been a strong demand from the industry for a stable concentrated solution that does not crystallize even at low temperatures especially in cold regions.
【０００４】しかしながら、本発明者らの知見による
と、農園芸用殺菌剤やスライムコントロール剤として従
来から一般的に使用されているエチレンビスジチオカル
バミン酸ナトリウム塩水溶液は、表１から０℃以下の低
温で、３２重量％以上の水溶液として結晶を析出しない
安定な状態で維持することが非常に困難である。However, according to the findings of the present inventors, the ethylene bisdithiocarbamic acid sodium salt aqueous solution conventionally generally used as an agricultural and horticultural fungicide or a slime control agent has a low temperature of 0 ° C. or less from Table 1. Therefore, it is very difficult to maintain a stable state in which crystals are not precipitated as an aqueous solution of 32% by weight or more.
【０００５】一方、特開平８−４１０１７号には、ジチ
オカルバミン酸塩の濃厚水溶液１００重量％に対して、
キサントゲン酸塩、チオ尿素、前記ジチオカルバミン酸
塩とは異なるジチオカルバミン酸塩の少なくとも一種を
０．５〜５重量％添加することによる低温安定性を有す
るジチオカルバミン酸塩水溶液が開示されているが、ジ
チオカルバミン酸塩濃厚水溶液にキサントゲン酸塩等を
添加することによる操作繁雑性及び品質上の問題、更に
それに伴う経済性に問題がある。On the other hand, JP-A-8-41017 discloses that a 100% by weight concentrated aqueous solution of dithiocarbamate is
An aqueous solution of dithiocarbamate having low-temperature stability by adding 0.5 to 5% by weight of at least one of xanthate, thiourea, and a dithiocarbamate different from the dithiocarbamate is disclosed. The addition of xanthate or the like to the concentrated salt aqueous solution has problems in operational complexity and quality, and furthermore in economic efficiency.
【０００６】[0006]
【発明が解決しようとする課題】エチレンビスジチオカ
ルバミン酸カルシウム塩を３０〜５０重量％含有し、０
℃以下の低温で晶析安定性を有するエチレンビスジチオ
カルバミン酸カルシウム塩水溶液を、他の薬剤の添加等
の操作繁雑性及び品質上の問題、更にそれに伴う経済性
に問題がなく斯界に提供することである。SUMMARY OF THE INVENTION 30 to 50% by weight of calcium ethylenebisdithiocarbamate,
To provide an ethylene bisdithiocarbamate calcium salt aqueous solution having crystallization stability at a low temperature of not more than ℃ without problems in operation complexity and quality, such as addition of other chemicals, and further, there is no problem in economics associated therewith. It is.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記の問
題に鑑み、解決すべく鋭意検討した結果、農園芸用殺菌
剤やスライムコントロール剤として従来から一般的に使
用されているエチレンビスジチオカルバミン酸ナトリウ
ム塩をエチレンビスジチオカルバミン酸カルシウム塩へ
変更することにより、その濃度を３０〜５０重量％とい
う高濃度で、しかも、０℃以下の低温でも外的刺激に対
して晶析しない安定性を有するエチレンビスジチオカル
バミン酸カルシウム塩水溶液を得ることに成功し、この
知見に基づき本発明を完成させるに至った。本発明に係
るエチレンビスジチオカルバミン酸カルシウム塩水溶液
は、エチレンビスジチオカルバミン酸金属塩を合成する
公知の方法を用いて製造できることから、他の薬剤との
混合を必要とせず、従ってそれに伴う操作繁雑性及び品
質上の問題、更に経済性に問題がないと考えられる。Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies to solve the above problems. By changing the sodium salt of dithiocarbamate to the calcium salt of ethylenebisdithiocarbamate, the concentration is as high as 30 to 50% by weight, and the stability that does not crystallize against external stimuli even at a low temperature of 0 ° C. or less. Succeeded in obtaining an aqueous solution of calcium ethylenebisdithiocarbamate having the above, and based on this finding, completed the present invention. Since the aqueous solution of calcium ethylenebisdithiocarbamate according to the present invention can be produced by using a known method for synthesizing a metal salt of ethylenebisdithiocarbamate, it does not need to be mixed with other chemicals, so that the operation is complicated and the operation is complicated. It is considered that there are no quality problems and no economic problems.
【０００８】本発明に係るエチレンビスジチオカルバミ
ン酸カルシウム塩水溶液の濃度は、３０重量％未満で
は、輸送や貯蔵等における経済性に不利であり、その濃
度が５０重量％を超えると、０℃以上でもエチレンビス
ジチオカルバミン酸カルシウム塩が晶析する恐れがあ
り、使用上問題がある。以下に、本発明の効果を実施例
に示すが、本発明の特許請求の範囲は実施例の態様に限
定されるものではない。[0008] If the concentration of the aqueous solution of calcium ethylenebisdithiocarbamate according to the present invention is less than 30% by weight, it is disadvantageous for economy in transportation and storage. Calcium ethylenebisdithiocarbamate may be crystallized, which causes a problem in use. The effects of the present invention will be described below with reference to examples, but the claims of the present invention are not limited to the embodiments.
【０００９】[0009]
実施例１ 本発明例のエチレンビスジチオカルバミン酸カルシウム
塩水溶液及び比較例のエチレンビスジチオカルバミン酸
ナトリウム塩水溶液は、公知の方法で合成し、それぞれ
の濃度は農薬取締法に基づく農薬公定検査法 −ジチオ
カーバメート剤（昭和２７年１１月告示）− に準拠し
て測定した。表１に示す結晶析出温度は、本発明例のエ
チレンビスジチオカルバミン酸カルシウム塩及び比較例
のエチレンビスジチオカルバミン酸ナトリウム塩の各水
溶液３０ｍｌ、その試料を入れる試験管（サイズ：直径
２５ｍｍ，長さ２８０ｍｍ）を用いて、ＪＩＳ Ｋ ０
０６５−１９９２（化学製品の凝固点測定方法）に準拠
して測定した。過冷却にて試料が晶析せず、安定化する
ことを避けるため、この試験の開始時から終了まで試料
を時々撹拌しながら行った。この理由として、過冷却で
安定化した試料をパイプ等で輸送時、刺激を受けて晶析
する恐れがあるためである。上記の測定結果を表１に示
した。Example 1 An aqueous solution of calcium ethylenebisdithiocarbamate of the present invention and an aqueous solution of sodium ethylenebisdithiocarbamate of Comparative Example were synthesized by known methods, and their concentrations were determined by the official pesticide inspection method based on the Pesticide Control Law-dithiocarbamate (Notified in November 1952). The crystal precipitation temperature shown in Table 1 is a test tube (size: 25 mm in diameter, 280 mm in length) in which 30 ml of each of an aqueous solution of the calcium salt of ethylene bisdithiocarbamate of the present invention and the sodium salt of ethylene bisdithiocarbamate of the comparative example are sampled. Using JIS K 0
The measurement was performed in accordance with No. 065-192 (method of measuring freezing point of chemical products). In order to prevent the sample from being crystallized and being stabilized by supercooling, the test was performed with occasional stirring from the start to the end of the test. The reason for this is that when the sample stabilized by supercooling is transported by a pipe or the like, there is a possibility that the sample may be crystallized by stimulation. Table 1 shows the above measurement results.
【００１０】[0010]
【表１】 ＊１） ＣａＥＤＣ：エチレンビスジチオカルバミン酸
カルシウム塩水溶液 ＊２） ＳＥＤＣ：エチレンビスジチオカルバミン酸
ナトリウム塩水溶液[Table 1] * 1) CaEDC: aqueous solution of calcium ethylenebisdithiocarbamate * 2) SEDC: aqueous solution of sodium ethylenebisdithiocarbamate
【００１１】[0011]
【効果】表１より０℃以下の結晶析出温度を有するため
には、比較例のエチレンビスジチオカルバミン酸ナトリ
ウム塩水溶液で３２重量％以下の濃度である。これに対
し、本発明例のエチレンビスジチオカルバミン酸カルシ
ウム塩水溶液は５０重量％以下の濃度で、しかも外的刺
激に対しても晶析しない安定な水溶液で維持できること
から、輸送や貯蔵等で経済的に有利に取り扱うことがで
きるものである。According to Table 1, in order to have a crystallization temperature of 0 ° C. or lower, the concentration of the aqueous solution of sodium ethylenebisdithiocarbamate of the comparative example should be 32% by weight or less. On the other hand, the aqueous solution of calcium ethylenebisdithiocarbamate of the present invention can be maintained at a concentration of 50% by weight or less and a stable aqueous solution which does not crystallize against external stimuli, so that it is economical for transportation and storage. It can be handled advantageously.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡辺 国雄 福島県須賀川市下宿前111番地大内新興化 学工業株式会社須賀川工場内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kunio Watanabe 111 Ouchi Emerging Chemical Industry Co., Ltd.
Claims (1)
ム塩を３０〜５０重量％含有し、０℃以下の低温でも晶
析安定性を有することを特徴とするエチレンビスジチオ
カルバミン酸カルシウム塩水溶液。1. An aqueous solution of calcium ethylenebisdithiocarbamate containing 30 to 50% by weight of calcium ethylenebisdithiocarbamate and having crystallization stability even at a low temperature of 0 ° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15422397A JPH10310570A (en) | 1997-05-09 | 1997-05-09 | Aqueous solution of calcium ethylenebis(thiocarbamate) having low-temperature crystallization stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15422397A JPH10310570A (en) | 1997-05-09 | 1997-05-09 | Aqueous solution of calcium ethylenebis(thiocarbamate) having low-temperature crystallization stability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10310570A true JPH10310570A (en) | 1998-11-24 |
Family
ID=15579549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15422397A Pending JPH10310570A (en) | 1997-05-09 | 1997-05-09 | Aqueous solution of calcium ethylenebis(thiocarbamate) having low-temperature crystallization stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10310570A (en) |
-
1997
- 1997-05-09 JP JP15422397A patent/JPH10310570A/en active Pending
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