CN114788518B - Stable aqueous suspension concentrate - Google Patents

Stable aqueous suspension concentrate Download PDF

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Publication number
CN114788518B
CN114788518B CN202110011442.6A CN202110011442A CN114788518B CN 114788518 B CN114788518 B CN 114788518B CN 202110011442 A CN202110011442 A CN 202110011442A CN 114788518 B CN114788518 B CN 114788518B
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aqueous suspension
suspension concentrate
thickener
calcium sulfate
concentrate according
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CN114788518A (en
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罗昌炎
詹姆斯.T.布里斯托
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Jiangsu Rotam Chemical Co Ltd
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Jiangsu Rotam Chemical Co Ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention provides a stable aqueous suspension concentrate containing a high content of copper calcium sulfate. The aqueous suspension concentrate contains: a) Copper calcium sulfate; b) One or more anionic surfactants, and the anionic surfactant has a pH of not less than 6; c) A thickener; d) Optionally one or more other conventional auxiliaries and additives; e) And water; and the conventional adjuvants and additives do not comprise nonionic surfactants. The technical scheme of the invention solves the problems of viscosity and fluidity of the water suspension system containing copper calcium sulfate. The aqueous suspension concentrate provided by the invention has no thickening and creaming phenomena in sanding and storage and has excellent storage stability.

Description

Stable aqueous suspension concentrate
Technical Field
The present invention relates to a stable aqueous suspension concentrate containing copper calcium sulphate; in particular to a stable aqueous suspension concentrate containing high content of copper calcium sulfate.
Background
Copper calcium sulfate (CuSO) 4 ·3Cu(OH) 2 ·3CaSO 4 ·7H 2 O) is an active ingredient which can be applied individually to the leaves for controlling plant pathogens as an inorganic compound containing copper ions.
The current commercial product of copper calcium sulfate comprises 77% copper calcium sulfate wettable powder, 77% copper calcium sulfate water dispersible granule, 40% copper calcium sulfate and 20% carbendazim wettable powder. The products containing copper calcium sulfate which are commercialized at present are all solid products. To date, there has been no successful commercial copper calcium sulfate-containing aqueous suspension concentrate.
An aqueous suspension concentrate is a liquid formulation containing a solid agrochemical active ingredient. An important issue to be considered in the design of agricultural formulation products is their stability. In addition to chemical instability that may occur during storage over time, physical stability problems are more often present.
When a water-insoluble solid pesticide is finely dispersed in water, the particles spontaneously aggregate due to their hydrophobicity and the presence of van der Waals attractive forces between the particles. According to the principle of colloid chemistry, such highly dispersed multiphase systems always spontaneously tend to merge smaller between particles, the total interfacial area decreases, the interfacial energy decreases, and finally the aqueous suspension is destroyed. The existing pesticide water suspending agent has at least the following situations due to physical instability, so that the suspending agent is flocculated, layered, creamed and the like:
(1) Flocculation and aggregation phenomena caused by interactions between particles;
(2) Oldham ripening (Ostwald ripening), a phenomenon of crystal growth of particles in the formulation;
(3) Delamination and particle deposition due to gravity.
When developing aqueous suspension concentrates containing calcium copper sulphate, the presence of high levels of inorganic substances leads to a very high tendency to develop thickening and creaming during sanding and storage. Therefore, the key to developing an aqueous suspension concentrate of calcium copper sulfate is to solve the viscosity and flowability problems of the system. It is clear that conventional dispersant systems do not solve the creaming problem. This makes it more challenging to develop stable copper calcium sulfate-containing aqueous suspension concentrates.
Disclosure of Invention
The present invention aims at overcoming the above disadvantages and providing a stable aqueous suspension concentrate which exhibits a very good fungicidal activity and which is effective in the preventive, therapeutic and eradication treatment.
The present invention provides an aqueous suspension concentrate comprising copper calcium sulphate, comprising:
a) Copper calcium sulfate;
b) One or more anionic surfactants, and the anionic surfactant has a pH of not less than 6;
c) A thickener;
d) Optionally one or more other conventional auxiliaries and additives;
e) And water;
and the conventional adjuvants and additives do not comprise nonionic surfactants.
The present invention provides an aqueous suspension concentrate comprising copper calcium sulphate which has sufficient bioactivity and storage stability without any adverse effects such as flocculation, stratification, creaming.
In a preferred embodiment, the aqueous suspension concentrate of the present invention comprises:
a) 500g/L-800g/L copper calcium sulfate;
b) 10g/L to 100g/L of one or more anionic surfactants, wherein the pH value of the anionic surfactant is not lower than 6;
c) 1g/L to 25g/L of thickener;
d) 0-250g/L of optionally one or more other conventional auxiliaries and additives;
e) Water is filled up to 1L;
the conventional adjuvants and additives do not comprise nonionic surfactants.
In a particularly preferred embodiment, the aqueous suspension concentrate of the present invention comprises:
a) 500g/L-800g/L copper calcium sulfate;
b) 20g/L to 80g/L of one or more anionic surfactants, and the pH value of the anionic surfactant is not less than 6
c) 1.3g/L to 15g/L of thickener;
d) 0-250g/L of optionally one or more other conventional auxiliaries and additives;
e) The water was made up to 1L.
The conventional adjuvants and additives do not comprise nonionic surfactants.
In a very particularly preferred embodiment, the aqueous suspension concentrate of the present invention comprises:
a) 500g/L-800g/L copper calcium sulfate;
b) 40g/L to 60g/L of one or more anionic surfactants, wherein the pH value of the anionic surfactants is not lower than 6;
c) 3g/L to 13g/L of thickener;
d) 0-250g/L of optionally one or more other conventional auxiliaries and additives;
e) The water was made up to 1L.
The conventional auxiliaries and additives do not contain nonionic surfactants, the thickener contains an organic thickener and an inorganic thickener, and the organic thickener and the inorganic thickener are in a specific mixing ratio with each other.
In the aqueous suspension concentrate according to the invention, the content of calcium copper sulphate as active ingredient is 500g/L to 800g/L, preferably 550 g g/L to 800g/L, more preferably 600g/L to 800g/L, particularly preferably 660g/L to 700g/L.
In the aqueous suspension concentrate of the present invention, suitable anionic surfactants are selected from salts of compounds such as alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.), ammonium, and various amines (e.g., alkylamines, cycloalkylamines, alkanolamines, etc.), and the like. Particularly preferred are sodium, potassium, triethanolamine salts of the following compounds:
carboxylic acid type surfactant: for example, polyacrylic acid, polymethacrylic acid, polymaleic acid, copolymers of maleic acid and olefins (e.g., isobutylene and diisobutylene, etc.), copolymers of acrylic acid and itaconic acid, copolymers of methacrylic acid and itaconic acid, copolymers of maleic acid and styrene, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methyl acrylate, copolymers of acrylic acid and vinyl acetate, copolymers of acrylic acid and maleic acid, N-methyl-fatty acid (C) 12 ～ 18 ) Sarcosinates, resin acids and fatty acids (C) 12 ～ 18 ) And the like, and salts of these carboxylic acids.
Sulfate type surfactant: examples thereof include alkyl (C) 12 ～ 18 ) Sulfate, polyoxyethylene alkyl (C) 12 ～ 18 ) Ether sulfate and polyoxyethylene (mono or di) alkyl C8 ～ 12 ) Phenyl ether sulphate, polyoxyethylene (mono-or di) alkyl (C) 8 ～ 12 ) Sulfate esters of polymers of phenyl ethers, sulfate esters of polyoxyethylene (mono-, di-or tri) phenyl ether, polyoxyethylene (mono-, di-or tri) benzyl phenyl ether, polyoxyethylene (mono-, di-or tri) styrylphenyl ether, sulfate esters of polymers of polyoxyethylene (mono-, di-or tri) styrylphenyl ether, sulfate esters of polyoxyethylene polyoxypropylene block polymers, sulfated oils, sulfated fatty acid esters, sulfate esters of sulfated fatty acids and sulfated olefins, and salts of these sulfate esters.
Sulfonic acid type surfactant: can be mentioned asFor example, paraffins (C) 12 ～ 22 ) Sulfonic acid, alkyl (C) 8 ～ 12 ) Benzenesulfonic acid, alkyl (C) 8 ～ 12 ) Formaldehyde condensate of benzenesulfonic acid, formaldehyde condensate of cresol sulfonic acid, alpha-olefin (C) 14 ～ 16 ) Sulfonic acid, dialkyl (C) 8 ～ 12 ) Sulfosuccinic acid, lignin sulfonic acid, polyoxyethylene (mono or di) alkyl (C) 8 ～ 12 ) Phenyl ether sulphonic acid, polyoxyethylene alkyl (C) 12 ～ 18 ) Ether sulfosuccinic acid half-esters, naphthalene sulfonic acids, (mono-or di) alkyl (C) 1 ～ 6 ) Naphthalene sulfonic acid, formaldehyde condensates of naphthalene sulfonic acid, (mono-or di) alkyl (C) 1 ～ 6 ) Formaldehyde condensate of naphthalene sulfonic acid, formaldehyde condensate of creosote sulfonic acid, alkyl (C) 8 ～ 12 ) Sulfonic acids such as diphenyl ether disulfonic acid, polystyrene sulfonic acid and copolymers of styrene sulfonic acid and methacrylic acid, and salts of these sulfonic acids.
Phosphate type surfactant: examples thereof include alkyl (C) 8 ～ 12 ) Phosphoric acid ester, polyoxyethylene alkyl (C) 12 ～ 18 ) Ether phosphate, polyoxyethylene (mono-or di) alkyl (C) 8 ～ 12 ) Phenyl ether phosphate, polyoxyethylene (mono-, di-or tri) alkyl (C) 8 ～ 12 ) Phosphate esters of polymers of phenyl ethers, phosphate esters of polyoxyethylene (mono-, di-or tri-benzyl phenyl ether phosphate esters, polyoxyethylene (mono-, di-or tri-styryl phenyl ether phosphate esters, phosphate esters of polymers of polyoxyethylene (mono-, di-or tri-styryl phenyl ether), phosphate esters of polyoxyethylene polyoxypropylene block polymers, phosphatidylcholine, phosphatidylethanolamine, condensed phosphoric acid (e.g., tripolyphosphoric acid, etc.), and salts of these phosphate esters.
Particularly preferred anionic surfactants in the aqueous suspension concentrate of the present invention are sodium, potassium, triethanolamine salts of the following compounds: alkylphenol ethoxylates, trisstyrylphenol ethoxylate phosphate, alkylphenol ethoxylate formaldehyde condensate sulfate, octylphenol ethoxylate sulfate, polyoxyethylene styrylphenyl ether sulfate, alkylphenol ethoxylates, castor oil ethylene oxide adducts, ethylene oxide-propylene oxide block copolymers, alkylphenol ethoxylate formaldehyde condensate, copolymers of styrene and methacrylic acid, lignin sulfonic acid, alkylbenzenesulfonic acid, alkylaryl sulfonic acid, alkyl naphthalene sulfonic acid, dialkyl sulfosuccinic acid.
Particularly preferred anionic surfactants in the aqueous suspension concentrate of the present invention are sodium, potassium, triethanolamine salts of compounds such as copolymers of styrene and methacrylic acid, trisstyrylphenol polyoxyethylene ether phosphate, alkyl naphthalene sulfonic acid, naphthalene sulfonic acid/formaldehyde condensate, alkyl benzene sulfonic acid, lignin sulfonic acid, polypropoxy polyethoxylate (block copolymers) and the like.
In the aqueous suspension concentrate according to the invention, the thickener is present in an amount of 1g/L to 25g/L, preferably 1.3g/L to 15g/L, more preferably 3g/L to 13g/L. The thickener comprises an organic thickener and an inorganic thickener.
The organic thickener suitable for the invention can be selected from xanthan gum, welan gum, diutan gum, carrageenan, guar gum, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, butyl acetate cellulose, polyvinyl alcohol, polyvinylpyrrolidone, alkali-swelling polyacrylic acid, pregelatinized modified starch, carboxypropyl guar gum, polyacrylamide and sodium polyacrylate; a preferred organic thickener is xanthan gum.
Inorganic thickeners suitable for use in the present invention may be selected from mineral fines such as magnesium aluminum silicate, montmorillonite, bentonite, hectorite or fumed silica, or alumina sols. Magnesium aluminum silicate is preferred because of its usefulness in small additions and ease of viscosity control.
In the aqueous suspension concentrate of the present invention, the organic thickener and the inorganic thickener are in a specific mixing ratio with each other. The weight ratio of the organic thickener to the inorganic thickener is 1:1-1:10, preferably 1:1.2-1:8, more preferably 1:1.8-1:8, more preferably 1:2.63-1:6, more preferably 1:2.63-1:5.36.
Optional one or more other conventional auxiliaries and additives are also included in the present invention. Such as antifreeze, defoamer, preservative, colorant, etc.
Antifreeze agents suitable for the present invention are selected from urea, glycols and polyols. Such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, etc. Propylene glycol and glycerin are preferred.
Suitable preservatives for the present invention are, for example, isothiazolinones. Such as 1, 2-benzisothiazolin-3-one, chloromethyl and methylisothiazolinone. Commercial products are CANGUARD ULTRA BIT, DOW), NIPACIDE CI MV, clariant).
Suitable antioxidants, defoamers, colorants, wetting agents, and the like are known to those skilled in the art.
The method for preparing the aqueous suspension concentrate of the present invention is particularly limited. The above components were added to water and mixed by a stirrer. Further, the pesticidal active ingredient, the dispersant and other auxiliary agents may be separately pulverized by a dry or wet pulverizer, respectively, or may be pulverized by a dry or wet pulverizer after mixing, as needed.
The dry grinding may be performed by an impact mill, a ball mill, a jet mill, or the like. The wet-grinding can be performed by wet-grinding machines such as an attritor, a sand mill, dai Nuomo, a bead mill, a Apex mill, a dispersion mill (visco mill) and an ultrafine dispersion mill (ultra visco mill).
In the aqueous suspension concentrate of the present invention produced by the above-described method, the copper calcium sulfate is ground and then dispersed in the form of suspended particles into the formulation, the average particle diameter of which is usually controlled in the range of 10um or less, preferably 0.5 to 5um, more preferably 0.5 to 3um, still more preferably 0.5 to 1.5um, particularly preferably 1.2 to 1.3um.
The aqueous suspension concentrate of the present invention can effectively control phytopathogenic fungi such as Plasmodium viticola (Plasmopara viticola) on vines, phytophthora on vegetables (Phytophthora spp.), pseudoperonospora cubensis (Pseudoperonospora cubensis) on cucurbitaceae, pythium on tobacco (Peronospora tabacina), bremia lactucae (Bremia lactucae) on lettuce and spinach, plasmodium (Ventum spp.) on fruit trees, leuconostoc on beans (Uromyces appendiculatus), alternaria spp.) on vegetables and fruit trees, moniliella (Sphaeroteca fuliginea) on cucurbitaceae, powdery mildew (Erysiphe spp.) on vegetables and cereals.
The aqueous suspension concentrate of the present invention is also effective in controlling bacterial diseases in plants without causing undesirable phytotoxic effects. Examples of plant bacterial diseases that can be effectively controlled by the aqueous suspension concentrate of the present invention include xanthomonas citri ulcer pathogenic bacteria (Xanthomonas campestris) of citrus, pseudomonas syringae tomato pathogenic varieties (Pseudomonas syringae pv tomato) of tomato plants, pseudomonas syringae kiwi pathogenic varieties (Pseudomonas syringae pv actinidiae) of kiwi plants, pseudomonas cucurbita moschata cucumber angular spot pathogenic bacteria (Pseudomonas lachrymans), xanthomonas campestris wild rape pathogenic varieties (Xanthomonas campestris pv campestris) of lettuce, pseudomonas aeruginosa (Pseudomonas viridiflava) of vegetables, walnut black spot pathogenic bacteria (Xanthomonas juglandis) of walnut trees, woodbacterium fastigiatum (xylella fastdiosa) of olive trees, and the like.
The aqueous suspension concentrate of the invention can be applied to plants or parts thereof, in particular to all parts of plants, to leaves, stems, branches and roots, or to the soil in which the plants are grown.
The aqueous suspension concentrate of the present invention exhibits excellent fungicidal activity and is useful for prophylactic, therapeutic and eradication treatments. And the aqueous suspension concentrate of the present invention is not any phytotoxic to the applied crop.
Detailed Description
The invention will be further illustrated with reference to examples.
Examples
Example 1
1. Dispersion of copper calcium sulfate
Magnesium aluminium silicate (trade name: VEEGUM R, from r.t. vanderbilt, 7.5g, alkyl naphthalene sulfonate [ trade name: dispersol BB4, from Croda ]45g, propylene glycol 50g, silicone defoamer [ trade name: SAG 1572, momentive 2g, 660g of a raw copper calcium sulfate (active ingredient concentration: 98%) was dispersed therein, and wet grinding was performed using 0.8-1.2mm phi glass beads with a sand mill [ Dynomill ] to obtain 1256g of a dispersion containing copper calcium sulfate.
2. Dispersing medium
Xanthan gum [ trade name: AG-RHO POL 23/W (CN source, from Solvay) 1.4g,1, 2-benzisothiazolin-3-one [ trade name: CANGUARD ULTRA BIT, from DOW ] 2.5g, chloromethyl and methylisothiazolinone [ trade name: NIPACIDE CI 15, 15 MV, from Clariant ]0.8g, 180g of a dispersion medium was obtained.
3. Preparation of aqueous suspension pesticidal composition
1256g of the copper calcium sulfate dispersion and 180g of the dispersion medium were mixed to obtain 1436g of the copper calcium sulfate aqueous suspension-type pesticide composition. The average particle diameter of the copper calcium sulfate is controlled to be 1.2-1.3um.
Example 2
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: the process was carried out in the same manner as in example 1 except that 45g of Dispersol BB4, from Croda was changed to a polycarboxylate (trade name: ATLOX METASERRESE 500L,from Croda]45g). The average particle diameter of the copper calcium sulfate is controlled to be 1.2-1.3um.
Example 3
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to a phosphoric acid ester amine salt [ trade name: SOPROPHOR FLK, from Solvay ]45g, and was produced in the same manner as in example 1. The average particle diameter of the copper calcium sulfate is controlled to be 1.2-1.3um.
Example 4
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to alkyl naphthalene sulfonate [ trade name: dispersol BB4, from Croda ]30g, amine phosphate salt [ trade name: SOPROPHOR FLK, from Solvay ]15g, and was produced in the same manner as in example 1. The average particle diameter of the copper calcium sulfate is controlled to be 1.2-1.3um.
Example 5
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to alkyl naphthalene sulfonate [ trade name: dispersol BB4, from Croda ]30g, polycarboxylate [ trade name: ATLOX meta process 500L,from Croda]15g, and the same method as in example 1 was used. The average particle diameter of the copper calcium sulfate is controlled to be 1.2-1.3um.
Example 6
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to a phosphoric acid ester amine salt [ trade name: SOPROPHOR FLK, from Solvay ]30g, polycarboxylate [ trade name: ATLOX meta process 500L,from Croda]15g, and the same method as in example 1 was used. The average particle diameter of the copper calcium sulfate is controlled to be 1.2-1.3um.
Example 7
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to a phosphoric acid ester amine salt [ trade name: SOPROPHOR FLK, from Solvay ]20g, polycarboxylate [ trade name: ATLOX metaperse 500L,from Croda]15g, alkyl naphthalene sulfonate [ trade name: dispersol BB4, from Croda ]10g. Except for this, the production was carried out in the same manner as in example 1. The average particle diameter of the copper calcium sulfate is controlled to be 1.2-1.3um.
Example 8
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to alkyl naphthalene sulfonate [ trade name: dispersol BB4, from Croda ]30g, was produced in the same manner as in example 1. The average particle diameter of the copper calcium sulfate is controlled to be 1.2-1.3um.
Comparative example 1
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to 45g of an acrylic surfactant [ trade name: EMULSON AGTRN 14105, from Zauba ]. A manufacturing process was performed in the same manner as in example 1.
Comparative example 2
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to 45g of an acrylic surfactant [ trade name: TERSPERSE2500, from HUNTSMAN ]. Except for the fact that the method was carried out in the same manner as in example 1.
Comparative example 3
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to a block polyether surfactant 45g [ trade name: pluronic PE6800, from BASF ], was produced in the same manner as in example 1.
Comparative example 4
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to a block polyether surfactant 45g [ trade name: SYNPERONIC T/908, from CRODA ], was produced in the same manner as in example 1.
Comparative example 5
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to polyoxyethylene tristyrylphenol ammonium sulfate salt (trade name: SOPROPHOR 4D384, from Croda; pH 3-5] 45g; produced in the same manner as in example 1; comparative example 6
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to alkyl naphthalene sulfonate [ trade name: dispersol BB4, from Croda ]30g, acrylate surfactant [ trade name: EMULSON AGTRN 14105, from Zauba ]15g, and the same procedure as in example 1 was followed. The average particle diameter of the copper calcium sulfate is controlled to be 1.2-1.3um.
Comparative example 7
Alkyl naphthalene sulfonate [ trade name ] of the dispersion of copper calcium sulfate in example 1: dispersol BB4, from Croda ]45g was changed to alkyl naphthalene sulfonate [ trade name: dispersol BB4, from Croda ]30g, and an ammonium salt of polyoxyethylene tristyrylphenol sulfate (trade name: SOPROPHOR 4D384, from Croda; pH 3-5]15g; the same method as in example 1 was used to prepare the copper calcium sulfate, the average particle size of which was controlled to 1.2-1.3. Mu.m.
Physical stability test
The sanding during sample preparation was observed and recorded. Placing the prepared water-based suspension pesticide composition into a 30ml volumetric vial, and preserving for 8 weeks in a constant temperature tank at 54 ℃; the mixture was left at room temperature for 24 hours. The viscosity of the freshly prepared sample and the viscosity after storage were measured. The results are shown in table 1. Each measurement was performed under the following conditions.
Viscosity measurement
The viscosity after 2 minutes from the start of the measurement was recorded using a type B VISCOMETER (manufactured by VISCOMETER DV-II+Pro, BROOKFIELD Co., ltd.) at a rotation speed of 30rpm with a rotor No. 2.
TABLE 1
The technical scheme of the invention solves the problems of viscosity and fluidity of the water suspension system containing copper calcium sulfate. The aqueous suspension concentrate provided by the invention has no thickening and creaming phenomena in sanding and storage and has excellent storage stability.

Claims (16)

1. A stable aqueous suspension concentrate comprising copper calcium sulfate, wherein the aqueous suspension concentrate comprises:
a) 500g/L-800g/L copper calcium sulfate;
b) 10g/L to 100g/L of one or more anionic surfactants, wherein the pH value of the anionic surfactant is not lower than 6;
c) 1g/L to 25g/L of thickener;
d) 0-250g/L of optionally one or more other conventional auxiliaries and additives;
e) Water is filled up to 1L;
the conventional adjuvants and additives do not comprise nonionic surfactants; the anionic surfactant is selected from salts of carboxylic acid type, sulfonic acid type and phosphate ester type compounds.
2. The aqueous suspension concentrate according to claim 1, wherein the aqueous suspension concentrate contains:
a) 500g/L-800g/L copper calcium sulfate;
b) 20g/L to 80g/L of one or more anionic surfactants, and the pH value of the anionic surfactant is not less than 6
c) 1.3g/L to 15g/L of thickener;
d) 0-250g/L of optionally one or more other conventional auxiliaries and additives;
e) Water is filled up to 1L;
the conventional adjuvants and additives do not comprise nonionic surfactants; the anionic surfactant is selected from salts of carboxylic acid type, sulfonic acid type and phosphate ester type compounds.
3. The aqueous suspension concentrate according to claim 1, wherein the aqueous suspension concentrate contains:
a) 500g/L-800g/L copper calcium sulfate;
b) 40g/L to 60g/L of one or more anionic surfactants, wherein the pH value of the anionic surfactants is not lower than 6;
c) 3g/L to 13g/L of thickener;
d) 0-250g/L of optionally one or more other conventional auxiliaries and additives;
e) Water is filled up to 1L;
the conventional adjuvants and additives do not comprise nonionic surfactants; the anionic surfactant is selected from salts of carboxylic acid type, sulfonic acid type and phosphate ester type compounds.
4. The aqueous suspension concentrate according to claim 1, wherein the thickener comprises an organic thickener and an inorganic thickener in a weight ratio of 1:1 to 1:10.
5. The aqueous suspension concentrate according to claim 1, wherein the thickener comprises an organic thickener and an inorganic thickener in a weight ratio of 1:1.2 to 1:8.
6. The aqueous suspension concentrate according to claim 1, wherein the thickener comprises an organic thickener and an inorganic thickener in a weight ratio of 1:1.5 to 1:6.
7. The aqueous suspension concentrate according to claim 1, wherein the thickener comprises an organic thickener and an inorganic thickener in a weight ratio of 1:2.63 to 1:5.36.
8. The aqueous suspension concentrate according to claim 1, wherein the thickener comprises an organic thickener selected from the group consisting of xanthan gum, welan gum, diutan gum, carrageenan gum, guar gum, hydroxyethyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose, carboxymethyl cellulose, butyl cellulose acetate, polyvinyl alcohol, polyvinylpyrrolidone, alkali swellable polyacrylic acid, pregelatinized modified starch, carboxypropyl guar gum, polyacrylamide, sodium polyacrylate, and inorganic thickeners.
9. The aqueous suspension concentrate according to claim 1, wherein the thickener comprises an organic thickener and an inorganic thickener, the inorganic thickener being selected from the group consisting of magnesium aluminum silicate, montmorillonite, bentonite, hectorite, fumed silica, alumina sol.
10. The aqueous suspension concentrate according to claim 1, wherein the anionic surfactant is selected from the group consisting of alkali metal, alkaline earth metal, ammonium or amine salts of carboxylic acid type, sulfonic acid type, phosphate type compounds.
11. The aqueous suspension concentrate according to claim 1, wherein the anionic surfactant is selected from the group consisting of sodium, potassium, triethanolamine salts of carboxylic, sulfonic, phosphate compounds.
12. The aqueous suspension concentrate according to claim 1, wherein the anionic surfactant is selected from the group consisting of copolymers of styrene and methacrylic acid, trisstyrylphenol polyoxyethylene ether phosphate, alkyl naphthalene sulfonic acid, naphthalene sulfonic acid formaldehyde condensate, alkyl benzene sulfonic acid, sodium, potassium salts of lignin sulfonic acid, triethanolamine salts.
13. Use of the aqueous suspension concentrate according to claim 1 for combating phytopathogenic fungi and bacteria.
14. A method of controlling phytopathogenic fungi and bacteria in crops by applying the aqueous suspension concentrate of claim 1.
15. The method of claim 14, wherein the aqueous suspension concentrate is applied to all parts of the plant or to the soil in which the plant is growing.
16. The method of claim 14, wherein the aqueous suspension concentrate is applied to the leaves, stems, branches and roots of the plant, or to the soil in which the plant is growing.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105475357A (en) * 2014-09-19 2016-04-13 江苏龙灯化学有限公司 Bactericidal composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105475357A (en) * 2014-09-19 2016-04-13 江苏龙灯化学有限公司 Bactericidal composition

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