CN1350788A - Aqueous suspanded chemical preparation - Google Patents
Aqueous suspanded chemical preparation Download PDFInfo
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- CN1350788A CN1350788A CN01137579A CN01137579A CN1350788A CN 1350788 A CN1350788 A CN 1350788A CN 01137579 A CN01137579 A CN 01137579A CN 01137579 A CN01137579 A CN 01137579A CN 1350788 A CN1350788 A CN 1350788A
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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
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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
- A01N25/22—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 ingredients stabilising the active ingredients
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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
- A01N25/30—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 characterised by the surfactants
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
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- Environmental Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
An aqueous suspension pesticide preparation of 1,1'-iminiodi(octamethylene)diguanidinium=tris(alkyl-benzenesulfonate), which not only has excellent storage stability under storage conditions where the temperature changes drastically in a long cycle through the seasons, but also excellent storage stability during storage in winter when the day and night short cycle temperatures fluctuate between 5 to -10 DEG C, further includes (b) a compound represented by the general formula (1): R-O-(CH2CH2O)n-H, (wherein R represents a C8-C18 alkyl group and n represents an integer of 0 to 4); (c) a phospholipid; (d) a surfactant having a C6-C20 alkyl group; and (e) water; and the phospholipid (c) is a hydrogenated phospholipid having an iodine value of less than 20.
Description
Technical field
The present invention relates to 1,1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate) for active ingredient, to low-temperature space periodically variations in temperature the aqueous suspanded chemical preparation of superior storage stability is arranged.
Background technology
The present invention relates to the active ingredient 1 of preparation, 1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate), it is a kind of good known horticultural bactericides (special fair 2-7564 communique of Japan, No. 4659739 patent of the U.S.), particularly the alkyl chain of alkylbenzenesulfonate has the composition of 12 carbon atoms to do that main composition uses, 1 of 10～13 carbon atoms are arranged, 1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate) (92～96 ℃ of fusing points) (being called as biguanides octyl benzene sulfonate) are being adopted by reality as a kind of wide spectrum horticultural bactericides.
Generally speaking, under the normal temperature the former medicine of solid pesticide is made under the occasion of aqueous suspension type preparation,, can be made floating type preparation (suspension) by being used in combination water-soluble or aqueous suspension synthetic high polymer and anion or nonionic surface active agent.
But for fusing point being the floating type preparation that 30～100 ℃ pesticide original medicine disperses to make, in case under the violent occasion of variations in temperature, place, solidify when dissolving during owing to the former medicine of dispersed solid, make the dispersity collapse so be accompanied by the growth of crystal.Even pesticide original medicine is dissolved in the common operable water-insoluble organic solvent, makes it in water emulsification and make suspension (emulsion, emulsion), also the fine droplet intercrystalline that can disperse in water because of pesticide original medicine is separated out crystallization and emulsion is destroyed.
As 1 of pesticide active ingredient use, 1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate) in the pesticide original medicine preparation processing, adopt known method of past significantly to separate out crystallization, are difficult to make the high suspension preparation of stability among the present invention.That is to say, for the floating type preparation that disperses to make, because above-mentioned pesticide active ingredient curing and crystallization are collapsed dispersity.And the dissolubility extreme difference of this pesticide active ingredient in available usually water-insoluble organic solvent, thereby be difficult to its emulsification.
For this reason, the inventor etc. develop a kind of aqueous suspanded chemical preparation, as the spy open record in the flat 8-225402 communique (No. 5728734, United States Patent (USP)), wherein contain: (a) 1,1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate), (b) compound of the general formula of using as dispersant (1) expression
R-O-(CH
2CH
2O)
n(in the formula, R represents that carbon number is 8～18 alkyl or alkenyl to-H, and n represents the integer between 0～4.) or phosphatide, (c) surfactant of 6～20 carbon atom alkyls or alkenyl is arranged, and (d) water.
This aqueous suspanded chemical preparation, under the big fierce condition of 50 ℃ of following long preservation tests ,-5 ℃ of following long preservation tests and the temperature difference, specifically evidence is preserved in the circulation during following 3 days at following 3 days of high temperature (50 ℃) and low temperature (10 ℃), after reaching long-term preservation of 12 weeks, pesticide active ingredients etc. can precipitation separation, keep altitude hold mode, thereby can be considered as be a kind of stability, the aqueous suspanded chemical preparation all high to environment and end user's safety.
Yet it is investigated that said preparation is to the bad adaptability of variations in temperature under the low temperature.Promptly, at cold zone, daytime and nocturnal temperature change in 5～-10 ℃ of scopes day after day in the winter time, if under this state with said preparation in the winter time during long preservation after 3～4 months, said preparation or remain under the high viscosity suspended state or be solidified into the paste shape does not recover good flow regime by the time spring temperature rises to about 20 ℃.Even and said preparation restores, its suspended state is variation also, and then separates out the small precipitate of pesticide active ingredient in agricultural chemicals, causes the spraying machine hole plug, makes to spill the medicine very difficulty that becomes.
Therefore, 1 of former exploitation, 1 '-imines two (eight methylene), two guanidine three (alkylbenzenesulfonate) aqueous suspanded chemical preparations, the cold zone in winter that under 0 ℃ of left and right sides low temperature of experience, repeatedly circulates, its storage stability be we can say abundant inadequately.
Disclosure of an invention
The problem that the present invention will solve is to provide 1, a kind of aqueous suspanded chemical preparation of 1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate), storage stability height when preserving under this preparation condition that not only variations in temperature is big in the long period between season, and the long preservation in winter that temperature changes in 5 ℃～-10 ℃ scopes in the short period between round the clock, also have advantages of excellent stability.
The inventor etc. have carried out various researchs for solving above-mentioned problem, found that: in above-mentioned prescription, if phosphatide adopts the hydrogenation phosphatide of iodine value below 20, then under the preservation condition that not only variations in temperature is big in the long period between season, and between round the clock in the short period temperature under the preservation condition of 5～-10 ℃ of range, can both keep stable suspended state, the small precipitate that suppresses pesticide active ingredient occurs, produce aqueous suspanded chemical preparation, thereby finished the present invention with good storage stability.
That is to say that the present invention provides a kind of aqueous suspanded chemical preparation in order to solve above-mentioned problem, wherein contains: (a) 1,1 '-imines two (eight methylene) two guanidinesalts=three (alkylbenzenesulfonate), (b) general formula (1)
R-O-(CH
2CH
2O)
n(in the formula, R represents that carbon number is 8～18 alkyl to-H, and n represents the integer between 0～4.) compound of expression, (c) phosphatide (d) has the surfactant of 6～20 carbon atom alkyls and (e) water; It is characterized in that wherein said phosphatide is that iodine value is the hydrogenation phosphatide below 20.
The best mode that carries out an invention
The constituent of next coming in order explanation aqueous suspanded chemical preparation of the present invention.
(a) composition 1 that the present invention uses, 1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate) are the pesticide active ingredients of aqueous suspanded chemical preparation of the present invention.
Constitute the alkylbenzenesulfonate that the present invention uses active ingredient, the benzene sulfonic acid of preferred 1～20 carbon atom alkyl, and the viewpoint from preventing that poisoning and drug effect are high, the benzene sulfonic acid of preferred especially 4～18 carbon atom alkyls of tool, the preferably benzene sulfonate of 10～13 carbon atom alkyls.These pesticide active ingredients (a) in fact all are water insoluble ingredients.Wherein alkylbenzenesulfonate has 1 of 10～13 carbon atom alkyls, and 1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate) are the farm chemical ingredients that is called " biguanides octyl benzene sulfonate ".
The compound (b) of general formula (1) expression below is described.
The compound of (b) above-mentioned general formula (1) expression of using among the present invention plays the dispersion stabilizer effect in aqueous suspanded chemical preparation of the present invention.
In the general formula (1), the compound of n=0 is the saturated fatty alcohol that does not have 8～18 carbon atoms of oxygen ethylidene in the molecule.
In the general formula (1), the compound of n=1 is that glycol ether is combined in the alcohol on the representative examples of saturated aliphatic alcohol molecule of 8～18 carbon atoms, be commonly referred to as polyoxyethylene (1 mole) monoalky lether, usually omit " list " word and directly be called polyoxyethylene (1 mole) alkyl ether.And the alcohol represented of for example so-called n=3, be meant that triethylene glycol ether is combined in the alcohol on the representative examples of saturated aliphatic alcohol molecule, is commonly referred to as polyoxyethylene (3 moles) alkyl ether.
The representative examples of saturated aliphatic alcohol of 8～18 carbon atoms can be straight or branched, preferred straight chain shape.And representative examples of saturated aliphatic alcohol preferred (a) and alkyl in the alkylbenzenesulfonate that constitutes pesticide active ingredient alcohol with same carbon atoms number, the straight chain alcohol of preferred especially 10～13 carbon atoms.
Representative examples of saturated aliphatic alcohol by above-mentioned general formula (1) expression, for example can enumerate straight chain alkanols such as octanol, decyl alcohol, laruyl alcohol, hexadecanol, octadecanol, (another name: diethylene glycol list-2-ethylhexyl ether) wait branched alkyl alcohol, polyoxyethylene such as polyoxyethylene (1～4 mole) cetyl ether number of repeat unit n partly is polyoxyethylene alkyl ether of 1～4 or the like for 2-Ethylhexyl Alcohol, 2-ethylhexyl diethylene glycol.
Below (c) iodine value of explanation the present invention use is at the hydrogenation phosphatide below 20.
(c) iodine value that the present invention uses plays dispersion stabilizer at the hydrogenation phosphatide below 20 in aqueous suspanded chemical preparation of the present invention.
Hydrogenation phosphatide of the present invention, be the lecithin that to produce by animality lipoid substances such as grain and oil seed such as soybean, vegetable seed and yolk, to iodine value to 20, utilize this method to make most of unsaturated fat acid moieties of phosphatide be transformed into the material of saturated fatty acid through hydrotreatment.Among the present invention the material of special use be that iodine value is lower than 10 hydrogenation phosphatide.
From iodine value and the little viewpoint of mass change that derives from natural goods, the soybean lecithin of preferred especially hydrogenation in these hydrogenation lipoid substances.
Through confirming, (c) iodine value of using among the present invention is widely used in cosmetics and field of food etc. less than 20 hydrogenation phosphatide, particularly hydrogenation lecithin and water soluble protein, and also high to the safety of environment and human body.Even, select to make the composition that applies some make up with the field of food use for general formula (1) the expression compound that uses among the present invention, the safety that can a nearly step improve the aqueous suspension preparation.In these compounds no matter which kind of, pesticide active ingredient all plays the dispersion stabilizer effect in aqueous suspension type preparation.
Next illustrates that (d) that use among the present invention has the surfactant of 6～20 carbon atom alkyls.
(d) that uses among the present invention has the surfactant of 6～20 carbon atom alkyls, both can be ionic, also can be nonionic.Constitute the alkyl of above-mentioned surfactant molecule, though can be straight or branched, more preferably straight chain shape.Constitute the alkyl of surfactant molecule, preferably with the alkyl benzene sulphonate molecules of salt that constitutes (a) farm chemical ingredients in alkyl, have same carbon atoms number, the more preferably alkyl of 10～18 carbon atoms, the alkyl of preferred especially 10～13 carbon atoms.
Angle from dispersion stabilization, alkyl in compound (b) molecule of the general formula that uses among the present invention (1) expression, and constitute alkyl in surfactant (d) molecule of 6～20 carbon atom alkyls, alkyl has the alkyl of same carbon atoms number, the alkyl of preferred especially 10～13 carbon atoms in all preferred and the alkyl benzene sulphonate molecules of salt that constitutes pesticide active ingredient.
Raw material with surfactant (d) use of 6～20 carbon atom alkyls, owing to come from natural materials mostly, the carbon number of its alkyl has certain distribution, so, then can use surfactant with 6～20 carbon atom alkyls so long as contain said preferred 10～18 carbon atom alkyls.
The operable surfactant (d) that 6～20 carbon atom alkyls are arranged among the present invention can be divided into five kinds of poly (oxyalkylene) base class nonionic surface active agent (d-1), fatty acid ester nonionic surface active agent (d-2), anionic surfactant (d-3), cationic surface active agent (d-4) and amphoteric ionic surfactants (d-5).
As poly (oxyalkylene) base class nonionic surface active agent (d-1), can enumerate for example polyoxyethylene (20 moles) lauryl ether, polyoxyethylene (15 moles) cetyl ether and so on polyoxy alkylidene ethers, the amino ethers of the polyoxy alkylidene of polyoxyethylene (12 moles) lauryl amino ethers and so on etc.
As fatty acid ester nonionic surface active agent (d-2), can enumerate for example SY-Glyster ML 750, ten glycerine myristates, six glycerine octadecane acid esters and so on poly-glycerine polyunsaturated fatty acid ester class, the alkyl diol polyunsaturated fatty acid ester class of birdsing of the same feather flock together of polyethylene glycol (mean molecule quantity 600) laurate, polyoxyethylene polypropylene glycol polyunsaturated fatty acid ester classes such as polyoxyethylene polypropylene glycol block copolymer stearate or the like.
As anionic surfactant (d-3), can enumerate for example NaLS and so on alkylsurfuric acid salt, polyoxyethylene (20 moles) Zetesol AP salt and so on laureth sulfate class etc.
As cationic surface active agent (d-4), can enumerate for example hexadecyltrimethylammonium chloride and so on alkylammonium salt, the polyxyethylated ammonium salt class of polyoxyethylene (10 moles) octadecyl methyl ammonium chloride and so on etc.
As amphoteric ionic surfactant (d-5), can enumerate for example lauryl dimethyl amido betaine and so on alkyl betaine class, lauryl dimethyl amino oxide and so on alkyl amino oxide etc.
In the above-mentioned surfactant, as the illustrative polyglycereol polyunsaturated fatty acid ester of the non-example type of fatty acid ester surfactant (d-2) class, because the low-temperature stability when its aqueous suspanded chemical is good and preferred especially.
For aqueous suspanded chemical of the present invention, adopt water soluble protein (f) can give its good storage stability.As water soluble protein (f), can enumerate for example lactoprotein, phytoprotein, animal protein etc., perhaps protein formulation from making by it, caseic alkali metal salts such as skim milk powder, whole milk powder, lactalbumin hydrolysate, casein, casein-sodium for example, more than one materials of selecting in lactalbumin, bean powder, fish powder, gelatin, white of an egg powder, the powdery yolk etc.Preferred especially betain sodium salt in these materials.
The ratio of pesticide active ingredient (a) in aqueous suspanded chemical preparation of the present invention preferably is in 1～45 weight % scope, especially preferably is in 5～40 weight % scopes.The ratio of compound (b) in aqueous suspanded chemical preparation of the present invention of general formula (1) expression preferably is in 0.5～10 weight % scope, especially preferably is in 1～8 weight % scope.And iodine value preferably is in 0.5～10 weight % scope less than 20 the ratio of hydrogenation phosphatide (C) in aqueous suspanded chemical preparation of the present invention, especially preferably is in 1～8 weight % scope.In addition, have the ratio of surfactant (d) in aqueous suspanded chemical preparation of the present invention of 6～20 carbon atom alkyls, preferably be in 0.5～10 weight % scope, especially preferably be in 1～8 weight % scope.And the ratio of water (e) in aqueous suspanded chemical preparation of the present invention preferably is in 25～97.5 weight % scopes, especially preferably is in 36～92 weight % scopes.In the aqueous suspanded chemical preparation of the present invention and under the occasion with water soluble protein (f), water soluble protein (f) is in the ratio of aqueous suspanded chemical preparation of the present invention, according to hydrogenation phosphatide and water soluble protein resultant meter, preferably be in 0.5～10 weight % scope, especially preferably be in 1～8 weight % scope.
In the aqueous suspanded chemical preparation of the present invention, the ratio between the compound (b) of pesticide active ingredient (a) and general formula (1) expression preferably is in 0.1: 1～90: 1 scopes by weight, especially preferably is in 0.6: 1～40: 1 scopes.And in the aqueous suspanded chemical preparation of the present invention, pesticide active ingredient (a) and iodine value be less than the ratio between 20 the hydrogenation phosphatide (c), preferably is in by weight in 0.1: 1～90: 1 scopes, especially preferably is in 0.6: 1～40: 1 scopes.In addition, in the aqueous suspanded chemical preparation of the present invention, pesticide active ingredient (a) and have ratio between the surfactant (d) of 6～20 carbon atom alkyls preferably is in 0.1: 1～90: 1 scopes by weight, especially preferably is in 0.6: 1～40: 1 scopes.
In aqueous suspanded chemical preparation of the present invention, be furnished with under the occasion of water soluble protein (f), pesticide active ingredient (a), and iodine value is less than 20 hydrogenation phosphatide (c) and the ratio between water soluble protein (f) resultant, preferably be in by weight in 0.1: 1～90: 1 scopes, especially preferably be in 0.6: 1～40: 1 scopes.And iodine value is less than 20 hydrogenation phosphatide (c) and the ratio between the water soluble protein (f), preferably is in by weight in 1: 0.1～1: 10 scope.
In the scope of not damaging effect of the present invention, can also add other any compositions in the aqueous suspanded chemical preparation of the present invention.Said other compositions can be enumerated for example antifreezing agent, preservative, pH regulator agent etc.
Said antifreezing agent can be enumerated for example ethylene glycol, propane diols, propylene glycol monomethyl ether and so on organic solvent and urea etc.Use under the occasion of antifreezing agent, in aqueous suspanded chemical preparation of the present invention, preferably allocate the water of 1/50～1/4 water amount of allocating into of replacement into.
When preparing aqueous suspanded chemical preparation of the present invention, each composition fully must be mixed.Surfactant (d) with 6～20 carbon atom alkyls, though usually full dose is added, but also a part can be added to the compound (b) of pesticide active ingredient (a), general formula (1) expression and iodine value less than among 20 the hydrogenation phosphatide (c), another part then adds among the water (e).The order by merging of each composition is not particularly limited outside dewatering, but in order to make easy mixed uniformly mixture, preferred order is less than 20 hydrogenation phosphatide (c) with the compound (b) of general formula (1) expression and iodine value, and after being mixed together with water soluble protein (f) in case of necessity, adding pesticide active ingredient (a) again and have the surfactant (d) of 6～20 carbon atom alkyls to mix.
The compound (b) of blended active ingredient (a), general formula (1) expression, iodine value preferably do not add the method for water (e) mixing simultaneously less than 20 hydrogenation phosphatide (c) with when the surfactant (d) of 6～20 carbon atom alkyls is arranged.The compound (b) of blended active ingredient (a), general formula (1) expression, iodine value be less than 20 hydrogenation phosphatide (c) with when the surfactant (d) of 6～20 carbon atom alkyls is arranged, preferably mixing under suitable heating.At this moment and since high temperature treatment cause easily painted, so treatment temperature preferably below 80 ℃, preferred especially 50～70 ℃.
Add water and make the method for muddy state, known method before can adopting.That is to say, can be exemplified below:
(1) water is added in the good compound (b) that contains the expression of pesticide active ingredient (a), general formula (1) of prepared beforehand, iodine value less than 20 hydrogenation phosphatide (c) with the surfactant (d) of 6～20 carbon atom alkyls is arranged, also contain in the mixture of water soluble protein (f) in case of necessity, use the homogenizer stirring method
(2) in the water that is dissolved with part surface activating agent (d), the compound (b) that contains pesticide active ingredient (a), general formula (1) expression, iodine value that adds prepared beforehand is less than 20 hydrogenation phosphatide (c) and remaining surface activating agent (d), the mixture that also contains water soluble protein (f) is in case of necessity used homogenizer stirring method etc.
Can also make the nearly step micronize of aqueous suspanded chemical preparation of the present invention with high-shear homogenizer and high-pressure emulsification machine etc.
It is investigated, the dispersant particle in the aqueous suspanded chemical preparation of the present invention that obtains like this, owing to comprise (b)～(d) composition, thereby can make pesticide active ingredient insoluble in water (a) form a kind of discrete particles with stable dispersion.
The average grain diameter of discrete particles in the aqueous suspanded chemical preparation of the present invention, the numerical value with laser diffraction and scattering formula particle size distribution device is measured preferably is in 0.1～20 micrometer range.In view of the particle diameter that can not measure with laser diffraction and scattering formula particle size distribution device below 0.1 micron, even and the average grain diameter of discrete particles is in below 0.1 micron and also can uses in aqueous suspanded chemical preparation, so the average grain diameter lower limit in the aqueous suspanded chemical preparation is not limited.
In addition, the viscosity of aqueous suspanded chemical preparation of the present invention preferably is in 50～5000mPas scope.Along with the compound (b) of general formula (1) expression, iodine value less than 20 hydrogenation phosphatide (c), have the surfactant (d) of 6～20 carbon atom alkyls and the increasing of water soluble protein (f) adding proportion of adding in case of necessity, the viscosity of aqueous suspanded chemical preparation has the tendency that increases, decapacitation makes outside the stability raising of discrete particles, the viscosity that increases suppresses the effect of discrete particles sedimentation in addition, and is more favourable from the stability of suspending agent.Yet the viewpoint of handling and diluting easily water easily during from use, the viscosity of aqueous suspanded chemical preparation is more preferred with 100～1000mPas.
Embodiment
Below will the present invention be described, but the present invention is not limited in these scope of embodiments with embodiment and reference examples.As long as short of particularly pointing out, wherein said " umber " and " % " all refer to " weight portion " and " weight % ".
[embodiment 1]
With 30 parts of biguanides octyl benzene sulfonates, 3.7 parts of laruyl alcohols, 2 parts of hydrogenation soybean lecithin (" ベ イ シ ス LP-20H " that The Nisshin Oil Mills, Ltd produces, iodine value=7.7), 0.5 part of casein-sodium, 4 part of six stearine and 5 parts of ethylene glycol mix, after 70 ℃ the homogeneous mixture is made in heating down, again this mixture is slowly added water while stirring under 50 ℃ of insulations, obtained 100 parts of suspending agents.In homogenizer, this suspending agent was stirred 10 minutes, obtained aqueous suspanded chemical preparation with 3000 rev/mins.
The average grain diameter of the aqueous suspanded chemical preparation that obtains surely with laser diffraction and scattering formula size distribution instrumentation, the result is 4.4 microns.And be 170mPas with the viscometric result of Brookfield viscometer (30 rev/mins/20 ℃).
[embodiment 2]
With 30 parts of biguanides octyl benzene sulfonates, 3.7 parts of laruyl alcohols, 2 parts of hydrogenation soybean lecithin (" ベ イ シ ス LP-20H " that The Nisshin Oil Mills, Ltd produces, iodine value=6.7), 0.5 part of lactalbumin hydrolysate (Wako Pure Chemical Industries, Ltd.'s product), 2 part of ten stearine and 5 parts of ethylene glycol mix, after 70 ℃ the homogeneous mixture is made in heating down, again this mixture is slowly added entry while stirring under 50 ℃ of insulations, obtained 100 parts of suspending agents.In homogenizer, this suspending agent was stirred 10 minutes, obtained aqueous suspanded chemical preparation with 3000 rev/mins.
The result who measures average grain diameter and viscosity similarly to Example 1 is respectively 5.2 microns and 780mPas.
[embodiment 3]
With 30 parts of biguanides octyl benzene sulfonates, 4 parts of laruyl alcohols, 2 parts of hydrogenation soybean lecithin (" ベ イ シ ス LP-20H " that The Nisshin Oil Mills, Ltd produces, iodine value=7.7), 4 parts of SY-Glyster ML 750s and 5 parts of ethylene glycol mix, after 70 ℃ the homogeneous mixture is made in heating down, again this mixture is slowly added entry while stirring under 50 ℃ of insulations, obtained 100 parts of suspending agents.In homogenizer, this suspending agent was stirred 10 minutes, obtained aqueous suspanded chemical preparation with 3000 rev/mins.
The result who measures average grain diameter and viscosity similarly to Example 1 is respectively 4.3 microns and 190mPas.
[embodiment 4]
With 30 parts of biguanides octyl benzene sulfonates, 5 parts of diethylene glycol list-2-ethylhexyl ethers, 2 parts of hydrogenation soybean lecithin (" ベ イ シ ス LP-20H " that The Nisshin Oil Mills, Ltd produces, iodine value=7.7), 0.5 part of casein-sodium, 4 part of six stearine and 5 parts of ethylene glycol mix, after 70 ℃ the homogeneous mixture is made in heating down, again this mixture is slowly added entry while stirring under 50 ℃ of insulations, obtained 100 parts of suspending agents.In homogenizer, this suspending agent was stirred 10 minutes, obtained aqueous suspanded chemical preparation with 3000 rev/mins.
The result who measures average grain diameter and viscosity similarly to Example 1 is respectively 3.5 microns and 280mPas.
[reference examples 1]
With 30 parts of biguanides octyl benzene sulfonates, 2 parts of laruyl alcohols and 2 parts of oleyl alcohol and 2 parts of oleyl alcohol, 2 parts of soybean lecithin (" ベ イ シ ス LP-20 " that The Nisshin Oil Mills, Ltd produces, iodine value=80), 2 part of ten stearine, 1.5 part of ten glyceryl oleate and 5 parts of ethylene glycol mix, after 70 ℃ the homogeneous mixture is made in heating down, again this mixture is slowly added entry while stirring under 50 ℃ of insulations, obtained 100 parts of suspending agents.In homogenizer, this suspending agent was stirred 10 minutes, obtained aqueous suspanded chemical preparation with 10000 rev/mins.
The result who measures average grain diameter and viscosity similarly to Example 1 is respectively 3.2 microns and 480mPas.
[reference examples 2]
With 30 parts of biguanides octyl benzene sulfonates, 4 parts of laruyl alcohols, 2 parts of soybean lecithin (" ベ イ シ ス LP-20 " that The Nisshin Oil Mills, Ltd produces, iodine value=80), 4 part of ten stearine and 5 parts of ethylene glycol mix, after 70 ℃ the homogeneous mixture is made in heating down, again this mixture is slowly added entry while stirring under 50 ℃ of insulations, obtained 100 parts of suspending agents.In homogenizer, this suspending agent was stirred 10 minutes, obtained aqueous suspanded chemical preparation with 10000 rev/mins.
The result who measures average grain diameter and viscosity similarly to Example 1 is respectively 4.4 microns and 250mPas.
[reference examples 3]
30 parts of biguanides octyl benzene sulfonates, 4 parts of laruyl alcohols, 2 parts of yolk lecithins (are produced with the pure medicine of light Co., Ltd., iodine value=60), 4 part of ten stearine and 5 parts of ethylene glycol mix, after 70 ℃ the homogeneous mixture is made in heating down, again this mixture is slowly added entry while stirring under 50 ℃ of insulations, obtained 100 parts of suspending agents.In homogenizer, this suspending agent was stirred 10 minutes, obtained aqueous suspanded chemical preparation with 10000 rev/mins.
The result who measures average grain diameter and viscosity similarly to Example 1 is respectively 5.2 microns and 340mPas.
[reference examples 4]
With 30 parts of biguanides octyl benzene sulfonates, 5 parts of dipropylene glycol single-butyl ethers, 2 parts of soybean lecithin (" ベ イ シ ス LP-20 " that The Nisshin Oil Mills, Ltd produces, iodine value=80), 4 parts of SY-Glyster ML 750s and 5 parts of ethylene glycol mix, after 70 ℃ the homogeneous mixture is made in heating down, again this mixture is slowly added entry while stirring under 50 ℃ of insulations, obtained 100 parts of suspending agents.In homogenizer, this suspending agent was stirred 10 minutes, obtained aqueous suspanded chemical preparation with 3000 rev/mins.
Measure average grain diameter and viscosity behind the aqueous suspanded chemical suspending agent for preparing immediately similarly to Example 1, the result is respectively 10.8 microns and 1090mPas.Yet 40 ℃ leave standstill 3 after, separate and to separate out out yellow thick material, lost stable dispersant state.
Preservation test under (test example 1) hot conditions
The aqueous suspanded chemical preparation of preparation is placed 500 milliliters of vials, put into 50 ℃ of thermostats, leave standstill and placed for 12 weeks.Below carried out various tests, result of the test is shown among the table 1.
" storage stability test "
The outstanding turbid state of observation sample when preservation has suffered.And then under 20 ℃, preserved 24 hours, observe the restorative of outstanding turbid state.
Result of the test is estimated according to following standard.
◎: outstanding turbid state is fabulous, and pesticide active ingredient disperses well in water.
Zero: outstanding turbid in good condition, only found slightly lamination, but held with the hand vibration on the upper strata
Device is uniformly dispersed easily once more.
△: outstanding turbid state is poor slightly, and a part of suspension is the thickness state attached on the chamber wall, still
If stir then dispersion again with glass bar.
*: outstanding turbid state difference, most suspended substances is gel, and part cohesion, promptly uses
Glass bar stirs and also is not easy to disperse again.
" crystallization separate out have or not "
Through 12 usefulness leave standstill after the preservation sample 20 ℃ keep 24 hours again after, dilute 500 times, have or not crystallization to separate out with observation by light microscope.
" sieve residue determination "
, after preserving 24 hours again under 20 ℃, 50 gram samples are diluted in 1 premium on currency through the sample after the preservation of 12 weeks.Make all sieves by 45 microns holes of this dilution then.Then in sieve, inject 1 premium on currency, the horizontal vibration sieve, this washing operation repeats 5 times.Through measuring the composition of separating out on the screen cloth after the water washing, calculate the ratio that crystallization is separated out by following formula.
Crystallization eduction rate (weight %)=(separating out branch (gram))/(in the 50 gram samples
(a)+(b) addition+(c)+(d)+(f) (gram)) * 100 (what each symbol was represented respectively in the formula is (a) pesticide active ingredient weight, (b) general formula (1) expression compound weight, (c) iodine value is less than 20 hydrogenation phosphatide weight, (d) the surfactant weight of 6～20 carbon atom alkyls is arranged, (f) water soluble protein weight.)
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Reference examples 1 | Reference examples 2 | Reference examples 3 | |
| Storage stability (preserving when stopping) | ???◎ | ???◎ | ???◎ | ???○ | ???◎ | ???◎ | ???○ |
| Storage stability (after 20 ℃ of recoveries) | ???◎ | ???◎ | ???◎ | ???◎ | ???◎ | ???◎ | ???○ |
| What crystallization was separated out has or not | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
| Sieve residue rate (weight %) | ???0 | ???0 | ???0 | ???0 | ???0 | ???0 | ???0 |
Preservation test under (test example 2) high temperature, the low temperature cycling condition
The aqueous suspanded chemical preparation of preparation is placed 500 milliliters of vials, and 50 ℃ of constant temperature were preserved after 3 days, were cooled to-10 ℃ with 12 hours from 50 ℃, after 3 days, were warmed up to 50 ℃ with 12 hours from-10 ℃ in-10 ℃ of constant temperature preservations again.As a circulation (1 week), carried out the preservation test of 12 circulations (12 week) with this.Carried out storage stability test, crystallization equally with test example 1 and separated out and have or not test and sieve residue determination, result of the test is shown among the table 2.
The aqueous suspanded chemical preparation of reference examples 3 preparations has a little decorating film with on the chamber wall of ring-type attached to liquid level top when preserving termination.After recovering under 20 ℃, find that upper water separates.Sieve residue rate is 1 weight %.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Reference examples 1 | Reference examples 2 | Reference examples 3 | |
| Storage stability (preserving when stopping) | ? ???◎ | ? ???◎ | ? ???◎ | ? ???○ | ? ???○ | ? ???○ | ? ???△ |
| Storage stability (after 20 ℃ of recoveries) | ? ???◎ | ? ???◎ | ? ???◎ | ? ???◎ | ? ???○ | ? ???◎ | ? ???○ |
| What crystallization was separated out has or not | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
| Sieve residue rate (weight %) | ???0 | ???0 | ???0 | ???0 | ???0 | ???0 | ???1 |
Preservation test under (test example 3) cryogenic conditions
The aqueous suspanded chemical preparation of preparation is placed 500 milliliters of vials, preserved for 12 weeks for-5 ℃.Carried out storage stability test, crystallization equally with test example 1 and separated out and have or not test and sieve residue determination, result of the test is shown among the table 3.Though the aqueous suspanded chemical preparation of embodiment 3 preparations is the paste cure states when preserving the test termination, through but turning back under the good suspended state after 20 ℃ of recoveries.In contrast to this, the aqueous suspanded chemical preparation of reference examples 1 preparation part when preserving the test termination is the thickness state, even also finding the upper strata segregation phenomenon after 20 ℃ of recoveries, the sieve residue is with sieve pore blockade.The sieve residual rate reaches 2 weight %.
The aqueous suspanded chemical preparation of reference examples 2 preparations is paste when preserving the test termination, even also finding the upper water segregation phenomenon through 20 ℃ of recoveries, the sieve residue is with sieve pore blockade.The sieve residual rate reaches 2 weight %.
The aqueous suspanded chemical preparation of reference examples 3 preparations is paste when preserving termination, after recovering under 20 ℃, find the upper water segregation phenomenon, and the sieve residue is with sieve pore blockade.The sieve residual rate reaches 3 weight %.
Table 3
★ 1: present the paste solid state.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Reference examples 1 | Reference examples 2 | Reference examples 3 | |
| Storage stability (preserving when stopping) | ???◎ | ???◎ | ??_★1 | ???◎ | ???△ | ??_★1 | ??_★1 |
| Storage stability (after 20 ℃ of recoveries) | ???◎ | ???◎ | ???◎ | ???◎ | ???○ | ???○ | ???△ |
| What crystallization was separated out has or not | Do not have | Do not have | Do not have | Do not have | Have | Have | Have |
| Sieve residue rate (weight %) | ???0 | ???0 | ???0 | ???0 | ???2 | ???2 | ???3 |
Preservation test under (test example 4) low temperature cycling condition
The aqueous suspanded chemical preparation of preparation is placed 500 milliliters of vials, and 5 ℃ of following constant temperature were preserved after 6 hours, were cooled to-10 ℃ with 6 hours from 5 ℃, after 6 hours, were warmed up to 5 ℃ with 6 hours from-10 ℃ in-10 ℃ of preservations again.As a circulation (24 hours), carried out the preservation test of 84 circulations (12 week) with this.Carried out storage stability test, crystallization equally with test example 1 and separated out and have or not test and sieve residue determination, result of the test is shown among the table 4.
The aqueous suspanded chemical preparation of embodiment example 3 preparations though be the paste solid state, after recovering under 20 ℃, turns back under the good suspended state when preserving termination again.In contrast to this, the aqueous suspanded chemical preparation of preparation is the paste solid state in the reference examples 1,2 and 3 when preserving termination, even after recovering under 20 ℃, can not return under the good suspended state.Owing to this reason, the sieve residue will cause sieve pore blockade, full dose is filtered and can not once-through operation be finished, and carry out for three times but divide.Sieve residue rate is respectively 12 weight %, 9 weight % and 18 weight % for reference examples 1,2 and 3.
Table 4
★ 1: present the paste solid state.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Reference examples 1 | Reference examples 2 | Reference examples 3 | |
| Storage stability (preserving when stopping) | ???◎ | ???◎ | ??_★1 | ???◎ | ???_★1 | ??_★1 | ??_★1 |
| Storage stability (after 20 ℃ of recoveries) | ???◎ | ???◎ | ???◎ | ???◎ | ????× | ???× | ???× |
| What crystallization was separated out has or not | Do not have | Do not have | Do not have | Do not have | Have | Have | Have |
| Sieve residue rate (weight %) | ???0 | ???0 | ???0 | ???0 | ????12 | ???9 | ???18 |
Industrial applicibility
Preserve under the aqueous suspanded chemical preparation of the present invention preservation condition that not only variations in temperature is large in the long period between season, and preserve the winter that temperature changes in 5～-10 ℃ of scopes in the short period between round the clock, all have good storage stability.
Claims (6)
1, aqueous suspanded chemical preparation, wherein contain: (a) 1,1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate), (b) general formula (1)
R-O-(CH
2CH
2O)
nThe compound of-H (in the formula, R represents that carbon number is 8～18 alkyl, and n represents the integer between 0～4) expression, (c) phosphatide (d) has the surfactant of 6～20 carbon atom alkyls and (e) water; It is characterized in that wherein said phosphatide is iodine value less than 20 hydrogenation phosphatide.
2,, wherein also contain (f) water soluble protein according to the described aqueous suspanded chemical preparation of claim 1.
3, according to the described aqueous suspanded chemical preparation of claim 1, wherein constitute said (a) 1, the alkylbenzenesulfonate of 1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate), it is the benzene sulfonate that 10～13 carbon atom alkyls are arranged, and the compound of wherein said (b) general formula (1) expression, be have 10～13 carbon atom alkyls compound.
4, according to the described aqueous suspanded chemical preparation of claim 3, wherein said (d) surfactant is the surfactant with 10～13 carbon atom alkyls.
5, according to the described aqueous suspanded chemical preparation of claim 1, wherein constitute 1, the alkyl of the alkylbenzenesulfonate of 1 '-imines two (eight methylene), two guanidines three (alkylbenzenesulfonate), with the alkyl of the compound of general formula (1) expression and the alkyl that constitutes surfactant, be to have same carbon atoms number purpose alkyl.
6, according to the described aqueous suspanded chemical preparation of claim 1, the average grain diameter of dispersant particle in the aqueous suspanded chemical preparation wherein is in below 20 microns with the measured value of laser diffraction and scattering formula particle size distribution method.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP330431/2000 | 2000-10-30 | ||
| JP2000330431 | 2000-10-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1350788A true CN1350788A (en) | 2002-05-29 |
| CN1212770C CN1212770C (en) | 2005-08-03 |
Family
ID=18806954
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011375795A Expired - Lifetime CN1212770C (en) | 2000-10-30 | 2001-10-30 | Aqueous Suspanded Chemical Preparation |
Country Status (6)
| Country | Link |
|---|---|
| KR (1) | KR100764044B1 (en) |
| CN (1) | CN1212770C (en) |
| AU (1) | AU779666B2 (en) |
| BR (1) | BR0104887A (en) |
| IL (1) | IL146103A (en) |
| TW (1) | TWI241162B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103501603A (en) * | 2011-05-02 | 2014-01-08 | 巴斯夫欧洲公司 | A method for enhancing the performance of a pesticide with guanidines |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5437825A (en) * | 1977-08-30 | 1979-03-20 | Kureha Chem Ind Co Ltd | Controlling agents for spray in a small amount effective against blast and injurious insects in the paddy field at the same time. |
| JPS63290803A (en) * | 1987-05-22 | 1988-11-28 | Sumitomo Chem Co Ltd | Stable solid agricultural chemical formulation |
| JPH02279607A (en) * | 1989-04-18 | 1990-11-15 | Dainippon Ink & Chem Inc | Aqueous suspension-like biocidal composition |
| FR2670085B1 (en) * | 1990-12-10 | 1996-12-13 | Rhone Poulenc Chimie | PHYTOSANITARY SUSPENSIONS. |
| JP3233251B2 (en) * | 1995-02-23 | 2001-11-26 | 大日本インキ化学工業株式会社 | Aqueous suspension type pesticide formulation |
-
2001
- 2001-10-15 AU AU79420/01A patent/AU779666B2/en not_active Expired
- 2001-10-22 IL IL146103A patent/IL146103A/en active IP Right Grant
- 2001-10-24 TW TW090126254A patent/TWI241162B/en not_active IP Right Cessation
- 2001-10-29 KR KR1020010066719A patent/KR100764044B1/en active IP Right Grant
- 2001-10-30 CN CNB011375795A patent/CN1212770C/en not_active Expired - Lifetime
- 2001-10-30 BR BR0104887-2A patent/BR0104887A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103501603A (en) * | 2011-05-02 | 2014-01-08 | 巴斯夫欧洲公司 | A method for enhancing the performance of a pesticide with guanidines |
Also Published As
| Publication number | Publication date |
|---|---|
| IL146103A0 (en) | 2002-07-25 |
| CN1212770C (en) | 2005-08-03 |
| AU7942001A (en) | 2002-05-02 |
| AU779666B2 (en) | 2005-02-03 |
| KR100764044B1 (en) | 2007-10-09 |
| TWI241162B (en) | 2005-10-11 |
| KR20020033542A (en) | 2002-05-07 |
| BR0104887A (en) | 2002-09-10 |
| IL146103A (en) | 2006-10-31 |
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