DE2256757A1 - LIQUID COMPOSITION OF A DIFFICULT SUBSTANCE OR SUBSTANCES THAT AFFECT LIVING ORGANISMS - Google Patents

Description

Hamburg, the 14th November 197 2 129972

Priority: November 16, 1971, Japan,

Pat. Note No. 91074/1971

Applicant;

Kureha Kagaku Kogyo K.K.

8, 1-chome, Nihonbashi Horidome-cho, Chuo-ku,

Tokyo / Japan

Liquid composition with a difficult to dissolve substance that affects living organisms or Fabrics of this type

The invention relates to a low viscosity, im Liquid state composition or mixture containing a living organism contains influencing substance which is solid at normal temperature and insoluble in water or solvents or difficult to dissolve, making it extremely difficult to process into a liquid state agent is. The substance or substances should be in a

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Liquid i ^ t be dispersed, the water, solvent and contains a surfactant to form a liquid composition or mixture, which is characterized in particular by the fact that it does not change the state of uniform dispersion of the substance Maintains over a long period of time and with sufficient certainty. Under a substance or one otoff, which influences living organisms, are here and in the following substances with an antibacterial, Insecticides, weed-killing or plant-influencing action understood, with at least one these effects should be present

In the past, living organisms were influencing agents that were insoluble or difficult to dissolve in solvents have been prepared and used, preferably in the form of powders or hydrates. However, to face the difficulties to be avoided when handling powders and particularly the methods recently developed for the application of the smallest amounts is to be further improved It is extremely desirable for the consumers of these substances to put the substances in the state of a liquid composition bring to"

However, it has so far proven impossible to obtain a composition in the liquid state with to produce a substance that affects living organisms,

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if no easily dissolving solvent for such a substance is available.

If there is a substance affecting such living organisms for which there is no effective solvent in its brought finely divided state and then dispersed in water after adding a suitable dispersant the first result is a liquid with an apparently good dispersion. Start after a while however, first the well-dispersed fine particles sink and due to the difference in gravity settle ο This leads to a phase separation which prevents the substance from being applied evenly »Even then, if the liquid is shaken or stirred up with the deposited substance, the original good state of dispersion, as is well known, cannot be restored.

The main object of the invention is to provide a well dispersed and long lasting liquid composition of any substance affecting living organisms aforementioned type to thereby eliminate the above-mentioned difficulties that hitherto in this field of Technology exist.

To solve this problem is through thorough research and 'experiments have been found that a composition

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maintains its stabilized and well-dispersed state even if the viscosity of the liquid composition is less than 100 cp (centipoise) if in a liquid composition composed of a substance influencing living organisms above type, water, solvent and surfactant a weight ratio between the discontinuous Phase and the continuous phase range in size from about 0.80 - 1.05 showing the volume of the continuous Phase 25 - 70% and the volume of discontinuous Stage is $ 30- $ 75 of the total.

If the severity ratio has a certain value outside the specified range of 0.80 - 1.05, the stability of the composition in the liquid state becomes worse, and the living one contained therein Organisms influencing substance is then subject to the secretion from the liquid system, whereby such Isolation can make use impossible in practice. If further the volume of the discontinuous Phase more than $ 75 of the total liquid composition in turn, the stability is deteriorated to an intolerable extent even if the weight ratio is within the useful limits given above, β under extreme conditions can again in this case a phase separation can be triggered.

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The term "discontinuous phase" as used herein refers to an emulsified phase made up of discontinuous liquid particles and dispersed solid particles. If, for example, solid particles are contained in an oil droplet dispersed in water Emulsion that is prepared from a solvent and water - ■ has been dispersed, the discontinuous phase consists essentially of solvent particles and solid particles with a continuous phase consisting entirely of water.

It is already known from US Pat. No. 2,765,255 that a composition or a mixture of water, solvent, surface-active substance and solid chemical particles can be kept in a stabilized state. However, the U.S. Patent relates to a fcastenartige composition having high viscosity, is prevented in the otherwise possible deposit of solid particles ₀ However, it is extremely difficult to treat such a paste-like composition as a chemical contained in the regular liquid state. It is practically impossible to apply them to living organisms to affect them in their actual state or, instead, in the form of a dilute liquid even with a slight degree of dilution.

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On the other hand, according to the invention, it is actually possible to use a liquid chemical in a manner that is simple to carry out to manufacture from a substance affecting living organisms, which is either extremely difficult in solvents to dissolve or instead can only be dissolved in a specially selected solvent of a rare type. the Invention provides the use of a solvent or solvents that are cheap and readily available when these are used in the composition provided according to the invention “In this case it is practical no detrimental deposition of the influencing substance in the liquid composition is to be feared, in addition has numerous advantages, such as outstanding homogeneity, extremely durable stability and light weight Manageability, in contrast to previously known, comparable influencing agents in the liquid state

'Homogeneity' is used in this description as such State of the liquid composition denotes in which, any part is essentially a constant Concentration of the substance influencing living organisms contains as an active substance «

In the case of a composition in the liquid state, a minor amount of deposited may be more effective Substance occur depending on the type of chosen

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surfactant. However, even in such a case, the discharged solid particles can easily recover in the composition in the liquid state are dispersed, so that it is extremely easy and convenient to use.

The liquid composition according to the invention contains fine solid particles of a living organism influencing substance which is insoluble or difficult to dissolve in solvents, dispersed in an emulsion consisting of a solvent which is difficult or impossible to dissolve in water, water and a surfactant «. In this liquid composition, the weight ratio between the discontinuous phase and the continuous phase is set so that it is in a specially selected range of 0.80-1.05. In addition, the volume of the continuous phase is 25-10fo of the total volume of the liquid composition , while the volume fraction of the discontinuous Phawe is between $ 30 and $ 75. Finally, a viscosity of less than 100 cp is chosen for the liquid

The solvent used can be a mixture of two or more solvents that are insoluble in water or difficult to solve. The surfactant can, ie afterwards, be nonionic or anionic. ';

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Optionally it can consist of a mixture of two or more surface-active agents. The fine divided particles of the influencing substance are kept in their emulsified state in an emulsion which from solvent, water and the surface-active agent consists «, the emulsion can either be an 01-in-water or water-in-oil emulsion.

The living organisms to be used according to the invention Affecting substance can be a solid substance at normal temperature, which can easily be finely pulverized and is insoluble or difficult to dissolve in water or commonly used solvents ο It is extremely difficult to to bring this substance into a liquid composition with and by customary means and processes. the If possible, the substance should have a high chemical stability in water »

Theoretically, there is no limit to the amount to be added to the water. However, if too large an amount of the substance is added in practice, the viscosity of the resulting liquid composition will be unacceptably increased, so that the practical usefulness may be markedly reduced Amount of solid substance provided that corresponds to *> 0 vol .- # or less,

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The particle size of the finely divided solid substance can preferably be 50 / U or less, with an average of 5 y \ x or less being advantageously provided «

The one or more solvents may kerosene,! Toluene, xylene., Chloroform, caves tetrachloride, ligroin, liquid paraffin, and / or the like _o be These substances are loess insoluble in water or difficult depending upon the physical properties and the added amount of the living organism affecting substance "

The surfactant or agents included in the invention liquid composition can be used, can be selected from the following group, depending on the type and properties of or <> the solvent and the influencing solid: Polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Polyoxyethylene acyl ester, oxyethylene-oxypropylene block polymer, fatty acid e.-glyceride and similar nonionic surfactants Substances, fatty acid salts, sulfuric acid esters higher alcohols, alkylbenzenesulfonate, alkylnaphthalene sulfonate, Naphthalenesulfonic acid / forraalin condensate or similar anionic surface-active substances, commercial emulsifiers and dispersants for

the production of agricultural chemicals "

The amount of the surface-active substance (s) added can usually and preferably be 1-20 wt .- #

The active substance contained in the composition according to the invention need not be limited to one kind, but may also comprise several, if necessary. In this case, at least one of the substances should be suspended in solid particles, the other or the other substances can be combined in water or solvent or both dissolved _e The liquid composition according to the invention can further contain one or more additives soluble in water or the solvent, For example, known stabilizers, antioxidants, coloring agents, fragrances, the active substance-promoting substances, paste material such as starch, gum arabic and / or polyvinyl alcohol.

The composition according to the invention can, after dilution, similarly to customary emulsions used in agriculture be used with water, but if necessary, it can also be used in its state of manufacture i.e. without dilution, can be applied to plants or similar objects «If necessary, the liquid composition can can also be processed as an aerosol.

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Several preferred numerical examples are given below given for a better understanding of the invention "

example 1

5g Polyoxyäthylenalkylarylätherj a nonionic surface active agent were dispersed in 50 ml ligroin "To this dispersion a phthalides (4, 5 ₉ 6 ₉ 7-tetrachlorophthalide) was added and well dispersed in ligroin were 20g. 35 ml of water were added to this dispersion and fully stirred into a uniformly dispersed liquid composition. This dispersion was of the oil-in-water type and consisted of a continuous and a discontinuous phase. The continuous phase consisted of water and the surfactant dissolved therein and had a specific gravity of about 1.0 * The discontinuous phase consisted of; Phthalide (.. Wt spec 0.72) (. _E specif 1.88 wt), and ligroin, and had a specific total weight of 0.93 "was determined from the following relationship:

(Weight of phthalide) + (weight of ligroin) (volume of phthalide) + (volume of ligroin)

Therefore, the ratio of the specific gravity between the discontinuous and the continuous phase of 0.93 _{c was} the volume of the continuous phase

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was 40 # of the total liquid composition o The Viscosity of the product was measured to be 65 cp.

Example 2

A solvent mixture of 26.3 ml of carbon tetrachloride and 23.7 ml of benzene became 3 g of sorbitol fatty acid ester added as a nonionic surfactant and stir well. To this solution, 22.5 g of the phthalide in its finely divided state was added to To achieve a uniform dispersion, to which a further 35 kI of water were then added. This mixture became sufficient shaken or stirred to form a uniform liquid composition in the form of a well-formed To achieve emulsion of the water-in-oil type. The continuous Phase was a mixed solvent of carbon tetrachloride and benzene and the surfactant dissolved therein with a specific gravity of 1.244, The phthalide and the water formed a discontinuous phase with an average specific weight of 1.223, Therefore, the weight ratio between the discontinuous and continuous phases was 0.98, and that Continuous phase volume was $ 53 of the total volume. The viscosity was measured to be 17 cp.

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Example 3

A solvent mixture of 30 ml of xylene and 25 ml of kerosene was 5 g of polyoxyethylene alkyl ether, a nonionic surfactant, added and agitated sufficiently. 20g of finely divided phthalide was added to this solution added and well dispersed · Then 30 ml of water was added and agitated evenly and thoroughly to to obtain a uniform liquid suspension with a viscosity of 87.4 cp,

Example 4

5g polyoxyethylene alkyl ether, a nonionic surface-active Medium, were dissolved in 27 ml of xylene. This solution was mixed with 20 g of a finely divided insecticide "NAC" (1-naphthyl-N-methylcarbamate) added and evenly dispersed therein to this dispersion was 50 ml of water added and agitated sufficiently to create a uniformly dispersed liquid composition having a viscosity of 92 cp.

Example 5

6r polyoxyethylene alkylaryl ether, a nonionic surface-active agent, was added to 50 ml of xylene, and 5g of finely divided TMTD (tetramethylthiuram disulfide) and 2.5g of "AEROSII, 200", in silicone oxide produced by Fiima Nippon Aerosil KK, were well dispersed in it, the dispersion were in good dispergierts "ra extent added _e

35 ml of water were then added and agitated well, a uniform, uniform liquid composition with a viscosity of 88 cp.

Example 6

To 73 ml of water, 9 # polyoxyethylene alkylaryl ether, a nonionic, surface-active agent, and 13k of the bactericidal gaptan (N-trichloromethylthio) -4-cyclohexene-1,2-dicarboxyimide were added and dispersed well and then in a vessel with a capacity of 180 ml filled for use as an aerosol. The jar was also filled under pressure with 18 ml of vinyl chloride monomer, 17 ml of liquefied gas, and 30 ml of liquefied freon and worked sufficiently to achieve a uniform, uniform liquid aerosol composition.

The compositions of Examples I ₁ 3 »4 and 5 can be used as with regular emulsions in the form of an aqueous dilution. In addition, the liquid compositions according to Examples 1-5 above can be used in the as-prepared state. The product from Example 6 can be processed in the form of an aerosol. The products of Examples 1, 3i ** ■ and 5 are oil-in-water emulsions, while Examples 2 and 2 provide water-in-oil emulsions. In all of these emulsions the active substance in its finely divided state is well dispersed in the liquid phase, eo that it is one

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well-developed, stabilized emulsion results in "

The following are test results of the various above embodiments of the liquid according to the invention Composition explained to the reliable stability the state of dispersion of the active substances contained therein To illustrate substance «.

For testing, the liquid composition was first filled into a hollow cylinder with a content of 500 ml * A first 50 ml sample was then taken using a pipette which was inserted into the liquid to a depth of 10 cm. For this first sample, the Amount of the active substance determined. A second sample of 50 ml was then taken from the hollow cylinder by means of a Pipette removed to a depth of Oj 5 - 1 cm, measured from the bottom of the cylinder, «on it the amount of the active substance contained in the sample was determined «

In the following Table 1, the amounts thus measured and denoted by (A) and (B) are in comparison indicated with the corresponding amount (G) of the active substance contained in the original dispersion was in the cylindrical for 48 hours before this The vessel had been kept «To illustrate the superior and extremely long-lasting stability of the liquid,

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composition according to the invention are the corresponding Ratios (A) / (C), (B) / (C) and (A) / (B) are given. A liquid comparative composition is used as a reference value used, which consists of 20g phthalide in the form of 2 / U-particles, 5g polyoxyalkylphenyl ether as a surface-active agent and 85g water was produced and for which the corresponding values are given *

(A) AC Table 1 t η is
(A) AB)
χ 100 Middle part
small size,
/ ^u Product after 1.003 V increase 1
) (B) AC) 99.6 2 example 1 1,014- 1.007 101.4- 2 Example 2 0.996 1,000 99.7 2 Example ^ 0.998 0.998 97.4 2 Example 4- 0.010 1,024 0.2 2 Comparative
material '4,500

Note »Sample (C) was measured at a height of 2 cm from the free liquid level, taken.

From this table it can be clearly seen that the composition according to the invention in the liquid state does not contain any shows noticeable deposit on the cylinder base after 48 hours since the bus boarding was made

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have passed «. The invention ensures an amazing, superior stability of the composition over a long period of time *

On the other hand, in the case of the comparison suspension, that almost the entire amount of the active substance contained therein was deposited on the container bottom, so that the suspension was not readily usable «Restoring the dispersion by shaking and stirring the. Deposits could indeed be achieved, "however the disadvantageous deposition started again immediately". Therefore this suspension could not used for the intended purpose.

Test results for the usefulness of a composition according to the invention are given below ₀

Example of the usability test

The following test was aimed at the usefulness of the composition according to the invention, which is described in this FaIL contained an effective substance to combat rice diseases,

In several porous pots with a diameter of 10 cm Waterfield rice plants of the SASANISHIKI cultivar raised and treated with an aqueous dilute suspension of the Table treated active substance to such an extent that the plant leaves are sufficient

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were moistened. After the leaf surfaces had dried and four days had elapsed, a suspension containing traces of Pyricularia Oryzae Gavara was sprayed onto these leaves for inoculation. The pots were placed in a place kept at 25-28C. Four days after the inoculation was counted the number of affected areas in the following proportions and sites: upper leaf / stem, 20 stems / pot and 3 pots / treatment "order that the level could in% of the disease sunt erdrückung be determined from the following formula:

1 - total number of areas covered

Extent of the disease , affected areas found ν ^ ₀₀ suppression ^ total number of in not

treated areas found affected areas

A 50 # strength aqueous suspension of rapeseed, which is a commercially available chemical with a content of 50 % by weight of phthalide, was used as a comparison material. The results are also given in Table 2 below.

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Table 2. Plants- 2256757 Results the exam with Effective
substance
Pjpm Diseases Dilution
factor 125
250 Disease
und oppression s-
factor _t % "Rapsid" -
Water suspension 4,000
2,000: 500 82.4
97.6 1,000 125
62.5 100.0 Liquid together
settlement after
example 1 1,600
3,200 25O 98.2
84.5 800 100.0

How from the table? can be seen, shows the erfindungsgeraässer liquid composition in this test example ■ Outstanding performance in suppressing rice disease at the same concentration of the active substance in comparison with a conventional aqueous chemical suspension «,

Further examples are given below to illustrate that the composition according to the invention; if to a certain extent a deposit of the effective Substance should show a superior redispersibility having·

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Example 7

2.5 g of polyoxyethylene sorbitan alkyl ester and 2.5 k sorbitan alkyl ester were added to 50 ml of Ligrcnn and sufficiently shaken and dispersed. This liquid was 20 g of the active substance phthalide supplied in finely divided state and uniformly dispersed "Then 3 *> ml. Of water is added and sufficiently agitated to a uniform liquid composition _0! After a long period of time lasting Abstehenlassen the composition was a certain deposit form·

By shaking and / or stirring up those containing the deposit However, liquid could be the state of dispersion easily restored to such an extent that the material was ready for use. This redis— Pergated state can be maintained for at least several hours to such an extent as it is for the intended purpose is required. The viscosity of the liquid composition was 32 cp.

Example 8

6 g of polyoxyethylene alkyl ether were added to 40 ml of liquid paraffin added and dispersed evenly by stirring 10g of phthalide was added finely divided and well dispersed within the paraffin. On that were 4-9 ml of water are added and agitated so that a liquid Composition was formed. This liquid confluence

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Sedimentation tended to form some deposit of the active substance contained therein after the composition had been kept undisturbed for an extended period of time. By shaking and / or stirring the composition could easily regain its fully dispersed state in which it was ready for immediate use, if necessary after dilution, if necessary, was ready «. The viscosity of the composition present in the liquid state was 95 cp ₀

Redispersion check ,

Examinations have been made to ensure the redispersibility— To investigate the ability of liquid compositions according to the invention, if they do show a certain degree of deposition of the active substance contained therein should. For this purpose a 50 nü. holding hollow cylinder filled with a liquid state composition according to the invention, plugged and kept undisturbed for a week. About the redispersibility of the liquid showing a slight deposit To determine the suspension, the cylindrical container was inverted in position and the number of rotations repeated counted the number of times it took for the precipitate to disappear completely and all fine particles of the active substance in the whole dispersed state, so that again a completely dispersed, uniform liquid suspension showed «.

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A liquid suspension of 20 g of phthalide with an average particle size of 10 yu, 2.5 g Folyoxyethylene sorbitan alkyl ester, 2.5g sorbitan alkyl ester, the latter two substances as surface-active agents, and 85 ml of water. In the same way it was another comparison suspension liquid made of 10g phthalide with an average particle size of 2.5g polyoxyethylene alkyl ether as a surfactant and 89 ml of water. These reference suspensions are in the following Table marked with (1) and (2) «

Table 3 Middle part
the size of the
effective
Substance,, \ x Liquid
composition Number of inversions
of the vessel 10 Example 7 2 10 Comparison (1) 150 2 Example 8 3 2 Comparison (2) 160

As can be seen from Table 3, the liquid composition is according to the invention by a particularly good redispersibility excellent.

In the following Table 4 are the severity ratios

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between the discontinuous and the continuous phase of the liquid composition according to the invention as well as the viscosity for several embodiments "are given for example.

9. Tabel 4th viscosity
in centipoise liquid
composition
after :
Example. Severe
ratio Volume fraction of
continuous
phase of the rivers
togeth- er
se ^ tion in % 65 ' 1 0.93 40 17th 2 0.98 53 37.4 3 1.04 35 92 4th 0.97 55 88 5 0.95 43 - 6th 1.01 49 32 7th 0.91 40 95 8th 1.00 35

- PATENT CLAIMS -

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Claims (9)

PATENT CLAIMS ίΐ) Composition in the liquid state of a solid substance which is difficult to dissolve and which affects living organisms, characterized by a Emulsion consisting of a solvent that is insoluble or difficult to dissolve in water, water or a surface-active solvent Agent and contains the substance influencing living organisms in fine particles, where the ratio of the specific gravity of the discontinuous and the continuous phase the liquid composition in the range of 0.80 - 1.05 and the volume fraction of the continuous phase 25-70;! s and that of the discontinuous phase 30-75 ^ of the total volume and the composition is one Has viscosity less than 100 cp. 2. Composition according to claim 1, characterized in that the particles of the solid substance have a size of 50 ax and less. J. Composition according to claim 2, characterized in that that the average particle size is 5 / U or less. 4. Composition according to claims 1-3 »characterized by a level of surfactant in the range 1-20 - 25 - 309821/1227 5. Composition according to claim '1-4, characterized by a solvent from the group: kerosene, toluene, xylene, chloroform, carbon tetrachloride, ligroin, liquid paraffin, liquefied petroleum gas or the like 6. Composition according to claim 1-5 »characterized by a combination of at least two solvents _o 7. Composition according to claims 1-6, characterized in that the surface-active agent is non-ionic or anion-active, _o 8. Composition according to claim 1-7, characterized by a surfactant. of the following group: polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Polyoxyethylene acyl ester, oxyethylene-oxypropylene block polymer, fatty acid monoglyceride and similar »nonionic surface-active substances, fatty acid salts, sulfuric acid esters higher alcohols, alkylbenzenesulfonate, alkylnaphthalene sulfonate, Naphthalenesulfonic acid, formalin condensate or similar anionic surface-active substances, commercially available emulsifiers and dispersants for the manufacture of agricultural chemicals. - 26 - 309821/122? 9. Use of a composition according to claims 1-8, as aerosols 309821/1227