JPS6148481B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a concentrated lime-sulfur mixture, and more specifically, a concentrated lime-sulfur mixture containing 0.05-10% of polyethylene glycol with a molecular weight of 190-2100 and a total sulfur concentration of 28%.
% or more concentrated lime sulfur mixture.

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 high-concentration products because the shipping costs are high. On the other hand, crystalline lime sulfur mixture is commercially available as a highly concentrated product of 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℃ 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 product that is as easy to use as a lime-sulfur mixture and has a high concentration.

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 By mixing polyethylene glycol with the mixture, a concentrated lime-sulfur mixture that is liquid at room temperature and difficult to crystallize at low temperatures was obtained, thereby completing the present invention.

In other words, the present invention mixes and dissolves polyethylene glycol, which is harmless as an agricultural chemical, into a concentrated lime-sulfur mixture, so 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, making it easy to use. The object of the present invention 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 instead of quicklime as the lime content, but the above ratio in terms of quicklime is required. In addition, if only the amount of water added is reduced from the above ratio of chemicals, the concentration of the solution after the reaction will be high and it will be in a crystalline state even at room temperature, and the workability will be poor, and furthermore, this is different from the intention of the present invention. Become something.

The concentrated lime-sulfur mixture obtained here has a total sulfur sulfur concentration of 28% or more and is liquid at room temperature.
If the total sulfur concentration is lower than this, it will be similar to a normal lime-sulfur mixture, and the concentration will be diluted and the economic value will decrease. On the other hand, commercially available crystalline lime sulfur mixtures have a high concentration of total sulfur sulfur, around 36%, but in addition to the above-mentioned disadvantages, they crystallize at room temperature during production, so it is difficult to operate in liquid form. In order to do this, it is necessary to maintain the manufacturing process at a high temperature, and when considering energy loss, operational difficulties, etc., there are many disadvantages to the ratio of total sulfur sulfur concentration. In consideration of these points, the concentrated lime-sulfur mixture of the present invention has a total sulfur sulfur concentration of 28 to 34%, preferably about 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, moreover, crystals form when left standing in a container. There are drawbacks such as the crystals grow into large lumps that are difficult to remove from the container, the crystals are agglomerated and difficult to dissolve, and the crystals have corners that easily damage the container, so a simple concentrated product alone is insufficient in terms of performance. be.

However, when water-soluble polymers were mixed with this concentrated lime-sulfur mixture, they noticed that their behavior at low temperatures changed, and as a result of testing the behavior of various water-soluble polymers, they found that urea-glycerin was not effective unless it was concentrated at a high concentration. Methylcellulose and ethylcellulose are difficult to dissolve, casein decomposes in lime-sulfur mixtures, gelatin foams and crystals do not redissolve well, polyvinylpyrrolidone forms crystals quickly and the crystal particles are large, inbutylene maleic anhydride copolymer Coalescence forms large crystals that are difficult to dissolve; polyacrylamide has poor solubility; sodium ligninsulfonate has poor solubility and has a narrow range of effectiveness; polyethyleneimine gradually grows into large crystals at low temperatures; carboxymethyl cellulose Polyethylene glycol has poor solubility and tends to crystallize at high concentrations, which does not meet the purpose of the present invention. However, it has been found that polyethylene glycol is stable at low temperatures in the form of a liquid or gel and is in a unique state.

In the present invention, the amount of polyethylene glycol 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
~10%, and this amount varies depending on the molecular weight of polyethylene glycol. In other words, low-molecular polyethylene glycol with a molecular weight of about 200 has little effect and requires a large amount, while polyethylene glycol with a molecular weight of about 2000 is effective in a small amount, but
The solubility of polyethylene glycol also decreases.
If the amount of polyethylene glycol to be mixed is too small, the effect will not be recognized, and if it is too large, there will be adverse effects such as high viscosity of the liquid and undissolved matter remaining. % and the molecular weight of polyethylene glycol is M, it is limited to the range expressed by 100/M<W<1000/M+5. Compounds whose main component is polyethylene glycol and which have almost similar performance, such as ethylene glycol, propylene glycol copolymers, or polyethylene glycol in which hydrogen is replaced with an alkyl group, may also be used in the present invention if polyethylene glycol is the main component. obtain.

As for the method of mixing polyethylene glycol with the concentrated lime-sulfur mixture, it is preferable to mix the polyethylene glycol directly into the concentrated lime-sulfur mixture without dissolving it in water so as not to lower the concentration of the concentrated lime-sulfur mixture. The mixing step may be any step between the reaction step of the concentrated lime sulfur mixture and the final pass step, as long as the polyethylene glycol can be sufficiently mixed and dissolved.

Since the concentrated lime-sulfur mixture obtained by the present invention has a concentration approximately 1.5 times higher than that of conventional lime-sulfur mixtures, the cost required for storage space, shipping costs, etc. is reduced. On the other hand, in terms of quality, it was difficult to use the concentrated lime sulfur mixture in cold regions because it formed into large lumps of crystals in the container when it was cold, making it difficult to use in cold regions. In the case of a sulfur mixture, it is in a liquid or gel state at low temperatures and can be easily taken out from the container, and the concentrated lime-sulfur mixture that is taken out dissolves quickly and there is no difference in handling compared to conventional lime-sulfur mixtures. Furthermore, the polyethylene glycol 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 permeability.

Next, the concentrated lime-sulfur mixture of the present invention will be explained with reference to Examples.

Example 1 5.5 kg of quicklime, 10 kg of sulfur, and 7 kg of water were weighed and sold in a pressurized reaction vessel with an internal volume of 50 kg. The reaction vessel was rotated while blowing steam at a pressure of 7 kg/cm ² into the reaction vessel, and after 25 minutes, the steam was stopped at an internal pressure of 6.2 kg/cm ² and the rotation continued 65
After a few minutes, the reaction vessel is stopped and the reaction solution is taken out into a receiving tank.
The amount of drain from steam injection was 10.5 kg. The reaction solution was filtered through a high-pressure filter to obtain a concentrated lime-sulfur mixture as a solution. The physical properties of this liquid were a total sulfur concentration of 30.2% and a total lime concentration of 10.8%.

After adding 0.1 to 10% by weight of polyethylene glycols having different molecular weights to the above concentrated lime-sulfur mixture and dissolving the mixture, the conditions at 20°C and -5°C were examined. At 20°C, it is liquid within the range in which polyethylene glycol is dissolved, and there is no difference from that without the addition of polyethylene glycol. The state at -5°C is shown in Figure 1. -5
The experimental results at ℃ are shown in Figure 1. If the amount added is small, the lime-sulfur mixture will crystallize and be ineffective, but if it is 0.1 to 5% it will be liquid and effective, depending on the molecular weight of the polyethylene glycol. If the amount added is too large, undissolved residues of polyethylene glycol will remain, making it difficult to use the lime-sulfur mixture. The experimental results shown in FIG. 1 are within the scope of the present invention as long as they are effective in showing that polyethylene glycol is in a liquid or gel state at low temperatures.

[Brief explanation of the drawing]

Figure 1 shows the state of the concentrated lime-sulfur mixture at -5°C. The × marks are massive crystals. △ mark is gel-like. ○ marks are liquid. ● indicates undissolved residue of liquid polyethylene glycol. The shaded area indicates the claims of the present invention.

Claims (1)

[Scope of Claims] 1 Polyethylene glycol with a molecular weight of 190 to 2100 100/M<W<1000/M+5 W: Weight % of polyethylene glycol M: Concentrated lime with a total sulfur concentration of 28% or more containing molecular weight of polyethylene glycol Sulfur mixture. 2 The raw material composition other than polyethylene glycol is
Sulfur: quicklime: water weight ratio 1:0.5 to 0.55:1.5
The concentrated lime-sulfur mixture according to claim 1, wherein the concentration is 1.8.