JPS6141887B2 - - Google Patents
Info
- Publication number
- JPS6141887B2 JPS6141887B2 JP11662178A JP11662178A JPS6141887B2 JP S6141887 B2 JPS6141887 B2 JP S6141887B2 JP 11662178 A JP11662178 A JP 11662178A JP 11662178 A JP11662178 A JP 11662178A JP S6141887 B2 JPS6141887 B2 JP S6141887B2
- Authority
- JP
- Japan
- Prior art keywords
- sulfur
- lime
- concentrated
- polyvinyl alcohol
- sulfur mixture
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 45
- JNVCSEDACVAATK-UHFFFAOYSA-L [Ca+2].[S-]SSS[S-] Chemical compound [Ca+2].[S-]SSS[S-] JNVCSEDACVAATK-UHFFFAOYSA-L 0.000 claims description 44
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 238000007127 saponification reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 235000012255 calcium oxide Nutrition 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は濃縮石灰硫黄合剤に関するもので、更
に詳しくはケン化度90％以上のポリビニルアルコ
ールを0.1〜２％含む全硫化態硫黄濃度28％以上
の濃縮石灰硫黄合剤に関するものである。
従来製造されている石灰硫黄合剤は、全硫化態
硫黄濃度22〜27％の液体で農業用殺菌剤として使
用されているが、低濃度の水溶液の為容器が嵩張
り製品保管に広い場所を必要とし、又運賃も高く
つく為濃度品の要求が強い。一方で石灰硫黄合剤
の高濃度品として結晶石灰硫黄合剤が市販されて
いるが、結晶が溶解しにくいこと、溶解残渣が残
ること夏季35℃以上では結晶が軟らかくなるこ
と、等により取り扱いにくく、高濃度品ではある
が使い易さの点から不充分である。
本発明の目的は上述の要求に従い石灰硫黄合剤
と同等の使い易さを保ち高濃度の製品を提供する
ことにある。
本発明者はこの目的の為濃縮石灰硫黄合剤の製
造条件を検討し、全硫化態硫黄濃度28％以上の石
灰硫黄合剤の高濃度品を得ると共に、この高濃度
の濃縮石灰硫黄合剤にポリビニルアルコールを混
合することにより常温で液状であり低温時結晶し
にくい濃縮石灰硫黄合剤を得てここに本発明を完
成するに至つた。
すなわち本発明は濃縮した石灰硫黄合剤中に農
薬として無害のポリビニルアルコールを混合溶解
することにより、常温では石灰硫黄合剤と同様に
取り扱うことが出来、低温時でも液状又はゲル状
であり使用時水を加えると容易に溶解する取り扱
い易い濃縮石灰硫黄合剤を得ることにある。
本発明に於ける濃縮石灰硫黄合剤の製造条件
は、反応釜に入れる薬品の比率を普通の石灰硫黄
合剤の場合には硫黄：生石灰：水の比率が１：
0.6：2.1近辺であるのに対し、濃縮石灰硫黄合剤
の場合この比率を１：0.5〜0.55：1.5〜1.8にして
反応させれば全硫化態硫黄濃度が28％以上のもの
が得られる。勿論石灰分として生石灰換算でなく
消石灰を用いてもよいが、生石灰換算で上記の比
が必要である。尚上記薬品の比率より添加する水
の量のみを少なくすると反応後の液の濃度が高く
なり常温でも結晶の状態になり作業性も悪く、し
かも本発明の意図とするものとは異なつたものに
なる。
ここに得られた濃縮石灰硫黄合剤は全硫化態硫
黄濃度28％以上で常温で液体のものであるが、こ
れより全硫化態硫黄濃度が低いと普通の石灰硫黄
合剤に近くなり、濃度的に希薄になり経済的価値
が少なくなる。逆に市販されている結晶石灰硫黄
合剤は全硫化態硫黄濃度は36％程度と高濃度であ
るが、これは前述の不利な点以外に製造時常温で
結晶化する為操作を液状で行なうには製造工程を
高温に保つ必要があり、エネルギーロス、操作上
の困難等を考慮すると、全硫化態硫黄濃度の割合
には不利な点が多い。本発明の濃縮石灰硫黄合剤
ではこれらの点を考慮して、全硫化態硫黄濃度は
28〜34％であり30％程度が望ましい。
しかし、ここに得られた濃縮石灰硫黄合剤は常
温では液体であり、普通の石灰硫黄合剤と同様の
取り扱いができるが、低温時結晶が析出し、しか
も容器中に静置しておくと結晶が成長し大きな塊
になり、容器から取り出しにくいこと、結晶が塊
のため溶解しにくいこと、結晶に角があり容器を
傷つけやすいこと等の欠点があり、単純な濃縮品
のみでは性能的に不充分である。
しかるに、この濃縮石灰硫黄合剤に水溶性高分
子を混合すると、低温での挙動が異なつてくるの
に気づき、種々の水溶性高分子につき挙動を試験
した結果、尿素グリセリンは高濃度でないと効果
がなく、メチルセルロース、エチルセルロースは
溶解困難、カゼインは石灰硫黄合剤中で分解す
る、ゼラチンは泡立つし結晶の再溶解が良くな
い、ポリビニルピロリドンは結晶生成が早く結晶
の粒子も大きい、イソブチレン無水マレイン酸共
重合体は大粒の結晶になり溶解しにくい、ポリア
クリルアミドは溶解性が悪い、リグニンスルホン
酸ソーダは溶解性が悪く効果のある範囲が狭い、
ポリエチレンイミン低温で除々に大きな結晶に生
長する、カルボキシメチルセルロースは溶解性が
悪くしかも高濃度では結晶し易すい、等により本
発明の意図に添わないが、ポリビニルアルコール
では低温で液状又はゲル状で安定していて特異な
状態にあることがわかつた。
本発明に於けるポリビニルアルコールの濃縮石
灰硫黄合剤に対する混合量は、低温時石灰硫黄合
剤が結晶になるのを防ぐに充分な量で、しかも出
来る限り少ない量が望ましく、一般的には0.1〜
２％の範囲である。ポリビニルアルコールを混合
する量は少なすぎると効果が認められないし、又
多すぎると液の粘度が高くなるとか、不溶解分が
残る等の悪影響がおきてくる。ポリビニルアルコ
ールにはケン化度により品質上の差があり、ケン
化度90％以下の部分ケン化ポリビニルアルコール
は濃縮石灰硫黄合剤に添加溶解後、−５℃に冷却
すると石灰硫黄合剤が結晶するので不適である。
これに対して、ケン化度90％以上の完全又は中間
ケン化ポリビニルアルコールでは低温時にも液状
を保ち安定している。
濃縮石灰硫黄合剤にポリビニルアルコールを混
合する方法は、濃縮石灰硫黄合剤の濃度を低く下
げない為に、ポリビニルアルコールを水に溶解し
ないで直接濃縮石灰硫黄合剤に混合する方法が望
ましいが、ポリビニルアルコールの濃縮石灰硫黄
合剤に対する溶解度が悪いので、ポリビニルアル
コールの高濃度の水溶液を作り混合してもよい。
混合する工程は、濃縮石灰硫黄合剤の反応工程か
ら最終過工程の間で、ポリビニルアルコールが
充分混合し溶解可能な工程であれば良い。
本発明により得られた濃縮石灰硫黄合剤は、従
来の石灰硫黄合剤に比較して濃度が約1.5倍にな
つているので、保管場所運賃等に要する経費が安
くなる。一方品質的には、石灰硫黄合剤の高濃度
品が寒冷時容器の中で大きな塊状の結晶になり、
容器から取り出せなくなり、寒冷地での使用は難
かしかつたが、本発明による濃縮石灰硫黄合剤の
場合低温では液状又はゲル状のため容易に容器か
ら取り出すことができるし、取り出した濃縮石灰
硫黄合剤の溶解も早く、取り扱い上従来の石灰硫
黄合剤と比較して差はない。又濃縮石灰硫黄合剤
中に含まれているポリビニルアルコールは、その
高分子の接着性の為農薬として植物に散布時展着
剤としての効果を増すことも期待できる。
次に本発明の濃縮石灰硫黄合剤を実施例にて説
明する。
実施例 １
生石灰5.5Kg、硫黄10Kg、水７Kgを内容積50
の加圧反応釜に秤取する。反応釜に圧力７Kg／cm2
の蒸気を吹きこみながら反応釜を回転し、25分後
に反応釜内圧6.2Kg／cm2で蒸気を停止し、回転を
続け65分後に反応釜を停止し、反応液を受槽に取
り出す。尚蒸気吹き込みによるドレン量は10.5Kg
であつた。反応液は高圧過器にて過し液と
して濃縮石灰硫黄合剤を得た。この液の物性は全
硫化態硫黄濃度30.2％、全石灰濃度10.8％、硫黄
対カルシユウムのモル比4.88、結晶開始温度13℃
であつた。
上記濃縮石灰硫黄合剤に中間ケン化ポリビニル
アルコール（ケン化度96.5±1.0％）を0.1、0.2、
0.5、１、２％添加して溶解した後、20℃及び−
５℃に於ける状態を調べた。
The present invention relates to a concentrated lime-sulfur mixture, and more particularly to a concentrated lime-sulfur mixture having a total sulfur concentration of 28% or more and containing 0.1 to 2% polyvinyl alcohol with a degree of saponification of 90% or more. Conventionally produced lime-sulfur mixture is a liquid with a total sulfur concentration of 22-27% and is used as an agricultural fungicide, but because it is a low-concentration aqueous solution, the container is bulky and requires a large space to store the product. There is a strong demand for concentrated products because the shipping costs are high. On the other hand, crystalline lime sulfur mixture is commercially available as a highly concentrated lime sulfur mixture, but it is difficult to handle because the crystals are difficult to dissolve, a dissolved residue remains, and the crystals become soft at temperatures above 35°C in summer. Although it is a highly concentrated product, it is insufficient in terms of ease of use. The object of the present invention is to meet the above-mentioned requirements and provide a highly concentrated product that is as easy to use as lime-sulfur mixtures. For this purpose, the present inventor studied the manufacturing conditions of concentrated lime-sulfur mixture, obtained a high-concentration product of lime-sulfur mixture with a total sulfur concentration of 28% or more, and The present invention was completed by mixing polyvinyl alcohol with a concentrated lime-sulfur mixture that is liquid at room temperature and difficult to crystallize at low temperatures. In other words, the present invention mixes and dissolves polyvinyl alcohol, which is harmless as an agricultural chemical, into a concentrated lime-sulfur mixture, so that it can be handled in the same way as a lime-sulfur mixture at room temperature, and remains liquid or gel-like even at low temperatures. The objective is to obtain a concentrated lime-sulfur mixture that is easily dissolved when water is added and is easy to handle. The production conditions for the concentrated lime-sulfur mixture in the present invention are as follows: In the case of a normal lime-sulfur mixture, the ratio of chemicals added to the reaction pot is 1: sulfur: quicklime: water.
While the ratio is around 0.6:2.1, in the case of a concentrated lime-sulfur mixture, if the ratio is 1:0.5-0.55:1.5-1.8 and the reaction is carried out, a total sulfur sulfur concentration of 28% or more can be obtained. Of course, slaked lime may be used as the lime content instead of in terms of quicklime, but the above ratio in terms of quicklime is required. If only the amount of water added is reduced from the above chemical ratio, the concentration of the solution after the reaction will be high and it will be in a crystalline state even at room temperature, resulting in poor workability and, moreover, a result different from the intention of the present invention. Become. The concentrated lime sulfur mixture obtained here has a total sulfur sulfur concentration of 28% or more and is liquid at room temperature, but if the total sulfur sulfur concentration is lower than this, it will be close to a normal lime sulfur mixture, and the concentration will be lower. It becomes diluted and its economic value decreases. On the other hand, commercially available crystalline lime sulfur mixtures have a high concentration of total sulfur sulfur, about 36%, but this has the disadvantages as well as the fact that it crystallizes at room temperature during production, so operations are performed in liquid form. It is necessary to maintain the manufacturing process at a high temperature, and considering energy loss, operational difficulties, etc., there are many disadvantages to the ratio of total sulfur sulfur concentration. Considering these points in the concentrated lime sulfur mixture of the present invention, the total sulfur sulfur concentration is
It is 28-34%, preferably around 30%. However, the concentrated lime-sulfur mixture obtained here is a liquid at room temperature and can be handled in the same way as a normal lime-sulfur mixture, but crystals precipitate at low temperatures and if left standing in a container. There are disadvantages such as the crystals grow and become large clumps that are difficult to remove from the container, the crystals are clumps that are difficult to dissolve, and the crystals have corners that easily damage the container. It is insufficient. However, when a water-soluble polymer was mixed with this concentrated lime-sulfur mixture, it was noticed that the behavior at low temperatures changed.As a result of testing the behavior of various water-soluble polymers, it was found that urea-glycerin is effective only at high concentrations. Methyl cellulose and ethyl cellulose are difficult to dissolve, casein decomposes in lime-sulfur mixture, gelatin foams and crystals do not redissolve well, polyvinylpyrrolidone forms crystals quickly and the crystal particles are large, isobutylene maleic anhydride Copolymers form large crystals and are difficult to dissolve, polyacrylamide has poor solubility, and sodium ligninsulfonate has poor solubility and has a narrow effective range.
Polyethyleneimine gradually grows into larger crystals at low temperatures, and carboxymethylcellulose has poor solubility and tends to crystallize at high concentrations, which does not meet the intent of the present invention, but polyvinyl alcohol is stable in liquid or gel form at low temperatures. I realized that I was in a peculiar situation. In the present invention, the amount of polyvinyl alcohol mixed with the concentrated lime-sulfur mixture is an amount sufficient to prevent the lime-sulfur mixture from crystallizing at low temperatures, and preferably as small as possible, and generally 0.1 ~
It is in the range of 2%. If the amount of polyvinyl alcohol mixed is too small, no effect will be observed, and if it is too large, adverse effects such as increased viscosity of the liquid and undissolved matter remaining will occur. There are quality differences in polyvinyl alcohol depending on the saponification degree. Partially saponified polyvinyl alcohol with a saponification degree of 90% or less is added to a concentrated lime-sulfur mixture and dissolved, and then cooled to -5℃, the lime-sulfur mixture crystallizes. Therefore, it is inappropriate.
On the other hand, completely or intermediately saponified polyvinyl alcohol with a degree of saponification of 90% or more remains liquid and stable even at low temperatures. Regarding the method of mixing polyvinyl alcohol with the concentrated lime-sulfur mixture, it is preferable to mix the polyvinyl alcohol directly into the concentrated lime-sulfur mixture without dissolving it in water in order to avoid lowering the concentration of the concentrated lime-sulfur mixture. Since polyvinyl alcohol has poor solubility in the concentrated lime-sulfur mixture, a highly concentrated aqueous solution of polyvinyl alcohol may be prepared and mixed.
The mixing step may be any step in which polyvinyl alcohol can be sufficiently mixed and dissolved between the reaction step of the concentrated lime-sulfur mixture and the final passing step. The concentration of the concentrated lime-sulfur mixture obtained by the present invention is about 1.5 times higher than that of conventional lime-sulfur mixtures, so the cost of storage space and other costs is reduced. On the other hand, in terms of quality, high-concentration products of lime-sulfur mixture form large lump-like crystals in containers during cold weather.
However, in the case of the concentrated lime sulfur mixture according to the present invention, it is liquid or gel-like at low temperatures, so it can be easily taken out from the container, and the concentrated lime The sulfur mixture dissolves quickly, and there is no difference in handling compared to conventional lime-sulfur mixtures. Furthermore, the polyvinyl alcohol contained in the concentrated lime-sulfur mixture can be expected to increase its effectiveness as a spreading agent when sprayed on plants as an agricultural chemical due to its polymeric adhesive properties. Next, the concentrated lime sulfur mixture of the present invention will be explained using Examples. Example 1 5.5 kg of quicklime, 10 kg of sulfur, 7 kg of water with an internal volume of 50
Weigh it into a pressurized reaction vessel. Pressure in reaction vessel 7Kg/cm 2
The reaction vessel is rotated while blowing in steam, and after 25 minutes, the steam is stopped at an internal pressure of 6.2 Kg/cm 2 , and rotation is continued until 65 minutes later, the reaction vessel is stopped and the reaction liquid is taken out into a receiving tank. The amount of drain by steam blowing is 10.5Kg.
It was hot. The reaction solution was passed through a high-pressure filter to obtain a concentrated lime-sulfur mixture. The physical properties of this liquid are: total sulfur sulfur concentration 30.2%, total lime concentration 10.8%, sulfur to calcium molar ratio 4.88, and crystallization onset temperature 13℃.
It was hot. Intermediately saponified polyvinyl alcohol (degree of saponification 96.5±1.0%) was added to the above concentrated lime sulfur mixture at 0.1, 0.2,
After adding and dissolving 0.5, 1, 2%, at 20℃ and -
The condition at 5°C was investigated.
【表】
20℃の状態ではポリビニルアルコールを混合し
ないものと変りないが、−５℃ではポリビニルア
ルコールを溶解した場合、0.1％ではゲル状0.2〜
２％では低温でも液状であるが、２％以上混合す
ると未溶解のポリビニルアルコールが増加してき
て使用は難かしい。
参考例
実施例１により得た濃縮石灰硫黄合剤に部分ケ
ン化ポリビニルアルコール（ケン化度88±２％）
を0.1〜２％添加して溶解した後、20℃及び−５
℃に於ける状態を調べた結果、20℃ではいずれも
液状であり未添加と変りないが、−５℃ではいず
れも結晶し大きな塊状になつた。[Table] At 20°C, it is the same as not mixing polyvinyl alcohol, but at -5°C, when polyvinyl alcohol is dissolved, at 0.1%, it becomes gel-like.
At 2%, it remains liquid even at low temperatures, but when it is mixed at 2% or more, undissolved polyvinyl alcohol increases, making it difficult to use. Reference example Partially saponified polyvinyl alcohol (saponification degree 88±2%) is added to the concentrated lime sulfur mixture obtained in Example 1.
After adding and dissolving 0.1 to 2% of
As a result of examining the state at 20°C, all of them were liquid at 20°C, the same as when no additive was added, but at -5°C, they all crystallized into large lumps.
Claims (1)
0.1〜２％含有する全硫化態硫黄濃度28％以上の
濃縮石灰硫黄合剤。 ２ ポリビニルアルコール以外の原料組成が硫
黄：生石灰：水の重量比で１：0.5〜0.55：1.5〜
1.8である特許請求の範囲第１項記載の濃縮石灰
硫黄合剤。[Claims] 1. Polyvinyl alcohol with a saponification degree of 90% or more
Concentrated lime-sulfur mixture containing 0.1-2% total sulfur sulfur concentration of 28% or more. 2 Raw materials other than polyvinyl alcohol have a weight ratio of sulfur: quicklime: water of 1:0.5 to 0.55:1.5
1.8, the concentrated lime-sulfur mixture according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11662178A JPS5543038A (en) | 1978-09-25 | 1978-09-25 | Concentrated lime sulfur mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11662178A JPS5543038A (en) | 1978-09-25 | 1978-09-25 | Concentrated lime sulfur mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5543038A JPS5543038A (en) | 1980-03-26 |
| JPS6141887B2 true JPS6141887B2 (en) | 1986-09-18 |
Family
ID=14691711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11662178A Granted JPS5543038A (en) | 1978-09-25 | 1978-09-25 | Concentrated lime sulfur mixture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5543038A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100461586B1 (en) * | 2001-12-12 | 2004-12-13 | 동원화학 주식회사 | The Preparation of Calcium Polysulfides |
| JP2017109996A (en) * | 2015-12-11 | 2017-06-22 | 日本合成化学工業株式会社 | Crystal growth inhibitor |
| JP2018065729A (en) * | 2016-10-21 | 2018-04-26 | 日本合成化学工業株式会社 | Liquid spraying agent for plant |
-
1978
- 1978-09-25 JP JP11662178A patent/JPS5543038A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5543038A (en) | 1980-03-26 |
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