CN116019093A

CN116019093A - Sanitary insecticidal suspending agent and preparation method thereof

Info

Publication number: CN116019093A
Application number: CN202211570990.3A
Authority: CN
Inventors: 闫阔; 冯立坤; 刘玉琢; 张羽宁
Original assignee: Jiangsu Work Is At Bio Tech Ltd
Current assignee: Jiangsu Work Is At Bio Tech Ltd
Priority date: 2022-12-08
Filing date: 2022-12-08
Publication date: 2023-04-28

Abstract

The invention relates to a sanitary insecticidal suspending agent and a preparation method thereof, wherein the sanitary insecticidal suspending agent comprises the following components in parts by weight: 0.1-40% of active component, 1.0-10% of wetting agent, 1.0-10% of dispersing agent, 0.05-10% of thickening agent, 1.0-10% of antifreezing agent, 0.1-1.0% of defoaming agent, 0.1-1.0% of preservative and water which are added to 100%. The suspending agent is combined by the optimized auxiliary agents, shortens the sanding time, ensures that the particle size of the drug particles is larger, has excellent wetting dispersion performance, and maintains better stability in the long-term standing process. The sanitary insecticidal suspending agent which is difficult to stabilize is more stable by selecting and selecting auxiliary agents such as a preferential wetting agent, a dispersing agent, a thickening agent and the like.

Description

Sanitary insecticidal suspending agent and preparation method thereof

Technical Field

The invention relates to the field of hygienic pesticides, in particular to a large-particle-size hygienic pesticide suspending agent containing pyrethroid, and a preparation method and application thereof.

Background

Pyrethroid pesticides are artificial synthetic pesticides which are increasingly popular in recent 30 years due to the advantages of broad insecticidal spectrum, good effect, low residue, no accumulation effect and the like. Besides preventing and controlling agricultural pests, the insecticidal composition has quite satisfactory killing effect in preventing and controlling pests of vegetables and fruit trees, public health mosquitoes, flies, cockroaches, head lice and the like.

The suspending agent is a sticky silk flowable suspension prepared by mixing pesticide raw materials, a carrier and a dispersing agent and carrying out superfine grinding by a wet method. The solid raw medicine which is insoluble or slightly soluble in water is uniformly dispersed in medium water by means of certain auxiliary agents through superfine grinding, so that a stable liquid-solid system with fine particles, high suspension and flowability is formed. The suspending agent is generally composed of an effective component, a dispersing agent, a thickening agent, an anti-settling agent, a defoaming agent, an antifreezing agent, water and the like. The processing of suspending agents has special requirements for pesticides: the solubility of the raw material in water is low, and the melting point of the solid raw material of the suspending agent system is preferably more than 60 ℃; the raw medicine has good chemical stability in water and is not easy to hydrolyze or decompose. The content of the effective components in the pesticide suspending agent is generally 5% -50%, generally, the finer the fineness is, the more uniform the distribution is, the higher the suspension rate is, and the fineness of the suspension rate in China is generally controlled to be about 1-5 mu m.

CN101953368A discloses a composition containing chlorofluoroether polyester and beta-cypermethrin, which is made into mosquito-repellent incense or insecticidal aerosol for preventing and controlling sanitary pests.

CN102630699a discloses a compound pesticide containing d-trans-cypermethrin and a compatible pesticide, wherein the compatible pesticide can be a lethal pyrethroid compound such as beta-cypermethrin, deltamethrin and the like, and is used for controlling sanitary pests.

CN107372578A discloses a sanitary insecticidal suspoemulsion containing a knockdown pyrethroid such as d-trans-cypermethrin, bifenthrin, transfluthrin, tefluthrin, methoprene or tefluthrin, and a lethal pyrethroid such as lambda-cyhalothrin, c-cyhalothrin, lambda-cyhalothrin, deltamethrin or bifenthrin for controlling sanitary pests.

CN114903050a discloses an insecticidal composition containing permethrin and beta-cypermethrin, which can be prepared into water dispersible granules and suspending agents for controlling sanitary pests.

CN114342953a discloses a deltamethrin suspending agent resistant to rain erosion, which comprises deltamethrin, wetting agent, dispersing agent, synergistic agent, thickening agent, preservative, antifreezing agent, suspending agent, defoaming agent and the balance of water.

CN112056322a discloses a sanitary insecticidal composition containing permethrin, said composition containing permethrin and a specific knockdown fluorinated pyrethroid, said composition having unexpected toxicity synergy compared to single dose, improving insecticidal effect.

The prior art has investigated the use of pyrethroids, or combinations of pyrethroids, in hygienic pests, including the preparation of suspensions. However, in practice, it is found that when the particle size of the suspending agent drug particles is properly increased, more drug particles can be prevented from penetrating through the surface of the target and penetrating into the target, so that more drug particles can be deposited on the surface of the target to achieve better control effects, and therefore, compared with the common suspending agent, the suspending agent has better long-acting retention activity and better rapid knockdown activity, and is very suitable for indoor and outdoor sanitary pest control. But the drug particles have larger particle size and the suspension rate can be reduced after long-term placement. Therefore, there is an objective need to find an excellent large-particle-size suspending agent formulation, thereby facilitating the stability of the formulation system and the full play of the drug effect.

Disclosure of Invention

The invention aims to overcome the problems in the prior art, and develops a suspending agent with large particle size and good preparation stability through compatibility screening of specific auxiliary agents, so as to solve the problem of reduction of quality indexes such as suspension rate and the like, thereby realizing the stability and good control effect of products.

The invention is completed by the following technical scheme.

The invention relates to a large-particle-size sanitary insecticidal suspending agent, which comprises the following components in percentage by mass:

wherein the mass percentage of each component is preferably as follows:

the mass percentage of each component is more preferably as follows:

in one large particle size sanitary insecticidal suspension formulation described herein, the active ingredient comprises a lethal pyrethroid and a knockdown pyrethroid. The lethal pyrethroid is selected from one or two of beta-cypermethrin or cis-cypermethrin. The knockdown pyrethroid is one or more selected from the group consisting of dextro-trans-cypermethrin, bifenthrin and permethrin. Specific combinations include, but are not limited to: beta-cypermethrin, D-trans-cypermethrin beta-cypermethrin and bifenthrin beta-cypermethrin and permethrin cis-cypermethrin, right-handed trans-cypermethrin, cis-cypermethrin, lambda-cyhalothrin and lambda-cyhalothrin. Wherein the ratio of lethal pyrethroid to knockdown pyrethroid may be 1:20-20:1, preferably 1:10-10:1, for example 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10).

In one embodiment of the present invention, the wetting agent is selected from polymer block polyether wetting agents, preferably one or more of Emulsogen 3510, atlox 4894, ethylan NS500LQ, ANTAROX BL-759, more preferably Ethylan NS500LQ or ANTAROX BL-759, most preferably ANTAROX BL-759.

In one embodiment of the invention, the dispersant is selected from the group consisting of phosphates, polycarboxylates, preferably a combination of phosphates and polycarboxylates. Wherein the phosphate dispersant is one or more selected from Soprophor SC, SP-SC3060, dispersogen LFS and YUS-FS3000, and is preferable; the polycarboxylate dispersant is one or more selected from GEROON T/36, agrilan752, SP-2728 and GY-D06. More preferably, the combination of dispersants comprises: soprophor SC+GEOPON T/36, soprophor SC+Agrilan 752, soprophor SC+SP-2728, soprophor SC+GY-D06, SP-SC 3060+GEOPON T/36, SP-SC3060+Agrilan752, SP-SC3060+SP-2728, SP-SC3060+GY-D06, dispersogen LFS+GEOPON T/36, dispersogen LFS+Agrilan 752, dispersogen LFS+SP-2728, dispersogen LFS+GY-D06, YUS-FS 3000+GEOPON T/36, YUS-FS3000+Agrilan 752, YUS-FS3000+SP-2728, YUS-FS3000+GY-D06. Preferred are combinations of Soprophor SC+GEROON T/36, soprophor SC+Agrilan 752, SP-SC3060+Agrilan752, dispersogen LFS+GEROON T/36, dispersogen LFS+SP-2728, YUS-FS3000+SP-2728, YUS-FS3000+GY-D06. More preferred is the combination of YUS-Fs3000+GY-D06 or YUS-Fs3000+SP-2728.

The weight ratio of the phosphate dispersant to the polycarboxylate dispersant is 1:10 to 10:1, preferably 1:5 to 5:1, more preferably 1:2.5 to 2.5:1, for example 1:2.5, 1:2, 1:1.5, 1:1, 1:1.5, 1:2, 1:2.5; most preferably 2.5:1.

In one embodiment of the present invention, the thickener is selected from one or two of xanthan gum, polyvinyl alcohol (PVA-1788, PVA-2088, PVA-2488), preferably xanthan gum, polyvinyl alcohol (PVA-1788, PVA-2088, PVA-2488) in a weight ratio of 1:5-5:1, preferably 1:3-3:1, more preferably 7:3.

The antifreezing agent is one or more selected from ethylene glycol, propylene glycol, glycerol and urea.

The defoamer is one or more selected from silicone oil, silicone compound, C10-20 saturated fatty acid and esters thereof, and C8-12 fatty alcohol defoamer.

The preservative is one or more selected from potassium sorbate, sodium benzoate, sodium diacetate, sodium dehydroacetate, pinocembrol, bronopol and the like.

The invention obtains proper auxiliary compatibility through preliminary screening and formula screening of auxiliary agents such as wetting agent, dispersing agent, thickening agent and the like, solves the technical contradiction that the particle size in the suspending agent is enlarged and the suspension stability is deteriorated, prepares the large-particle suspending agent formula with excellent quality indexes such as suspension rate, stability and the like, has the particle size D90 of 15-20 mu m, has the particle size range which is obviously larger than the particle size of the conventional suspending agent, and has the effect superior to the conventional suspending agent in the specific fields such as sanitation and disinsection and the like through the verification of a drug effect test.

The invention also relates to a preparation method of the large-particle-size sanitary insecticidal suspending agent, which comprises the following steps:

a. mixing the active ingredients with wetting agent, dispersing agent, thickening agent, antifreezing agent, defoamer, preservative and proper amount of water according to the formula proportion, and fully and uniformly shearing;

b. grinding the obtained mixture to particle diameter D90 of 15-20 μm, and filtering.

In particular, in the preparation method of the large-particle-size sanitary insecticidal suspending agent, the temperature is preferably controlled below 40 ℃ in the grinding process.

Another aspect of the present invention relates to the use of the above-described large particle size sanitary insecticidal suspension concentrates, in particular, sanitary insect pests including cockroaches, fleas, ants, bed bugs, mosquitoes or flies, which can be used for control. Preferably for absorbing surfaces such as cement surfaces, lime surfaces. The specific application method, the dosage and the like can be determined by the person skilled in the art according to the actual situation.

Compared with the prior art, the invention has the beneficial effects that:

(1) Compared with the conventional particle size suspending agent, the large-particle size sanitary insecticidal suspending agent disclosed by the invention has better long-acting retention activity and better quick knockdown activity.

(2) The invention forms a stable super network structure by selecting auxiliary agents such as wetting agent, dispersing agent, thickening agent and the like for compatibility, so that the suspending agent is not separated from water and layered in the long-term placing process, the system is uniform, and solid particles are not easy to agglomerate and Oryza curing.

(3) The invention adds a new formulation for the field of domestic sanitary insect disinfestation, has obvious drug effect and can be widely popularized and applied.

Detailed Description

The invention is further illustrated by the following specific examples, without limiting the invention to these specific embodiments.

The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.

Emulogen 3510, dispersogen LFS, used in the examples below, were purchased from Clariant, atlox 4894 from He, ethylan NS500LQ, agrilan752 from Ackersu-Norbeol, ANTAROX BL-759, sopro phor SC, GEROON T/36 from Solvin, SP-SC3060, SP-2728 from Optimu, YUS-FS3000 from Zhu Ben oil and fat, GY-D06 from Guangdong Yinong. Other raw materials are all readily available products on the market.

First, wetting agent and dispersant preliminary screening

And (3) carrying out primary screening on the wetting agent and the dispersing agent by adopting a flow point method.

The specific wetting agents tested included: emulsogen 3510, atlox 4894, ethylan NS500LQ, ANTAROX BL-759, SP-1600P;

the specific dispersants tested included: soprophor SC, SP-SC3060, dispersogen LFS, YUS-FS3000, GEROON T/36, agrilan752, SP-2728, GY-D06, FTRT DS523, SD-661;

the specific test method comprises the following steps: firstly, various wetting agents and dispersing agents are prepared into 5% aqueous solution for standby. Then, 2.0g of the ground active drug of beta-cypermethrin was weighed into a 20mL beaker and weighed. Then, the aqueous solution prepared as described above was mixed by ultrasonic waves while being dropped until the paste just slipped down along the wall of the beaker, the dropping was stopped, and the weight of the beaker was weighed again. The mass of the aqueous solution used (difference in mass measured 2 times) was calculated and averaged 3 times. Then, the mass of the solution used by the beta-cypermethrin with unit mass is calculated, namely the flow point value of the wetting dispersant to the tested raw medicine, and the specific calculation method is shown in the following formula (I).

The preliminary screening results of the above wetting agents are shown in table 1 below.

TABLE 1 wetting agent prescreening results

Sequence number	Wetting agent	Flow Point (g/g)
			1	Emulsogen 3510	0.74
2	Atlox 4894	0.79
			3	Ethylan NS 500LQ	0.69
4	ANTAROX BL-759	0.63
			5	SP-1600P	1.35

Screening results showed that Emulogen 3510, atlox 4894, ethylan NS500LQ, ANTAROX BL-759 were small, all below 0.8, which is advantageous; of these, ethylan NS500LQ and ANTAROX BL-759 are more preferred, with ANTAROX BL-759 being most preferred.

The preliminary screening results of the above dispersants are shown in table 2 below.

TABLE 2 dispersant Primary screening results

Sequence number	Dispersing agent	Flow Point (g/g)	Sequence number	Dispersing agent	Flow Point (g/g)
						1	Soprophor SC	0.95	6	Agrilan 752	0.94
2	SP-SC3060	0.92	7	SP-2728	0.82
						3	Dispersogen LFS	0.89	8	GY-D06	0.91
4	YUS-FS3000	0.86	9	FTRT DS523	1.36
						5	GEROPON T/36	0.93	10	SD-661	1.45

Screening results showed that the FTRT DS523, SD-661 had large flow points, both greater than 1.3, which was disadvantageous. The flow points of the rest of the dispersing agent are all between 0.8 and 1, but the dispersing agent is not ideal. Thus, further screening was performed on the dispersant combinations.

Based on the above preliminary screening results, each combination of phosphate dispersants and polycarboxylate dispersants (mass ratio of 2.5:1) was further screened, and the results are shown in Table 3 below.

TABLE 3 dispersant combination screening results

Of the above combinations of phosphate dispersants and polycarboxylate dispersants, the flow point of the combination of Soprophor SC+GEROON T/36, soprophor SC+Agrilan 752, SP-SC3060+Agrilan752, dispersogen LFS+GEROON T/36, dispersogen LFS+SP-2728, YUS-FS3000+SP-2728, YUS-FS3000+GY-D06 is preferably lower than 0.8; further, a combination of YUS-FS3000+SP-2728, YUS-FS3000+GY-D06 is more preferred; of these, the combination of YUS-Fs3000+GY-D06 is most preferred.

(two) preparation examples

According to the screening result, the following preparation formula is prepared, and the percentages of the invention are weight percentages unless otherwise indicated.

Example 1:10% cis-cypermethrin-bifenthrin large-particle-size sanitary insecticidal suspending agent

/>

Mixing the materials according to the formula proportion, fully shearing uniformly, grinding the obtained mixed solution until the particle diameter D90 is between 15 and 20 mu m, and filtering to obtain the product.

Example 2:10% high-efficiency cypermethrin-bifenthrin large-particle-size sanitary insecticidal suspending agent

Example 3:10% cis-cypermethrin-D-trans-cypermethrin large-particle-size sanitary insecticidal suspending agent

Example 4:10% high-efficiency cypermethrin-D-trans-cypermethrin large-particle-size sanitary insecticidal suspending agent

Example 5:10% high-efficiency cypermethrin-chlorpyrithrin large-particle-size sanitary insecticidal suspending agent

Example 6:10% cis-cypermethrin-permethrin large-particle-size sanitary insecticidal suspending agent

Example 7:10% high-efficiency cypermethrin-D-trans-cypermethrin large-particle-size sanitary insecticidal suspending agent

Example 8:10% cis-cypermethrin-bifenthrin large-particle-size sanitary insecticidal suspending agent

Comparative example 1:10% high-efficiency cypermethrin-D-trans-cypermethrin suspending agent

Comparative example 2:10% cis-cypermethrin-permethrin suspending agent

Comparative example 3:10% high-efficiency cypermethrin-D-trans-cypermethrin suspending agent

Comparative example 4:10% cis-cypermethrin-bifenthrin suspension

Comparative example 5:10% high-efficiency cypermethrin-chloreneyne pyrethrin suspending agent

/>

Comparative example 6:10% high-efficiency cypermethrin-D-trans-cypermethrin suspending agent

Example 4 was repeated except that the mixture was ground to a particle size D90 of about 3.0. Mu.m.

The various quality control indicators of the above examples and comparative examples were tested as follows: 1. the mass fraction of the effective components is measured by high performance liquid chromatography; 2. the pH was carried out according to CIPAC MT 75.3; 3. the suspension rate test method is carried out according to CIPAC MT 184; 4. wet sieve tests were performed in accordance with CIPAC MT 185; 5. persistent foaming was performed as CIPAC MT 47.2; 6. the heat storage stability is carried out according to 2.3 in GB/T19136-2003 (54 ℃,14 d), and the data after heat storage mainly test the suspension rate and the particle size; 7. pourability was performed according to CIPAC MT 148.1.

The quality specifications of the suspending agents of examples 1-8 are shown in Table 4.

TABLE 4 quality specifications of suspending agents of examples 1-8

/>

The quality specifications of the suspending agents of comparative examples 1-5 are shown in Table 5.

TABLE 5 comparative examples 1-5 suspension quality specifications

Test index	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Test basis
							Mass fraction of active ingredient	10.1	10.1	10.1	10.1	10.1	Liquid chromatography
pH	6.7	7.3	7.1	7.1	6.8	CIPAC MT 75.3
							Wet screening test, no less than	99	99	99	99	99	CIPAC MT 185
Persistent foamability after 1min	20	15	20	25	25	CIPAC MT 47.2
							Pourability of	3.8	3.5	3.3	3.4	3.3	CIPAC MT 148.1
Suspension ratio before heat storage	92.5	88.1	82.1	82.4	75.4	CIPAC MT 184
							Post heat storage suspension rate	90.1	86.3	79.4	79.1	72.1	CIPAC MT 184
Particle size before heat storage, D90, μm	15.4	16.1	16.6	15.7	16.3	Laser particle size analyzer
							Particle diameter D90, μm after heat storage	19.3	18.1	17.9	17.1	18.7	Laser particle size analyzer

The data show that each of examples 1-8 is excellent in quality index, wherein examples 4 and 6 are preferred, and example 4 is most preferred, and the reduction of the suspension rate before and after heat storage is minimal, and the particle size increase is small, namely the heat storage stability is good. Correspondingly, in comparative examples 1-2 and 4-5, after changing the wetting agent or the dispersing agent, various indexes such as thermal storage stability of the preparation are deteriorated; in comparative examples 3 and 5, the composite thickener of xanthan gum and polyvinyl alcohol was changed to magnesium aluminum silicate, and deterioration of various indexes such as thermal storage stability of the preparation was also observed. The comparison shows that the stability of the formulation of the preparation is excellent.

(III) biological assay

Control object: culex light color and housefly;

the test method comprises the following steps: retention spray test, in accordance with the indoor efficacy test of a hygienic insecticide for GBT 13917.1-2009 pesticide registration and evaluation part 1: residence and spray test in spray agent, measurement of knock-down time KT 30d after coating of absorbent surface ₅₀ And mortality.

Experimental treatment: diluting the preparations of examples 1-8 and comparative examples 1-6 with water 200 times to obtain spray solution, and mixing with the effective components 20mg/m ² Is used for measuring the knock-down time KT of 30d after coating ₅₀ And 24h mortality.

The results of the measurements on culex light and house flies are shown in tables 6-7 below.

TABLE 6 culex light-colored pharmacodynamic test results

TABLE 7 results of test of the efficacy of housefly

The above examples are only exemplary embodiments employed for the purpose of illustrating the present invention, and the present invention is not limited thereto. It will be appreciated by those skilled in the art that the invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.

Claims

1. The large-particle-size sanitary insecticidal suspending agent is characterized by comprising the following components in percentage by mass:

2. the large-particle-size sanitary insecticidal suspending agent according to claim 1, wherein the mass percentage of each component is preferably as follows:

3. a large particle size sanitary insecticidal suspension according to claim 1 or claim 2 wherein the active ingredients comprise lethal pyrethroid and knockdown pyrethroid in a weight ratio of 1:20 to 20:1; and, in addition, the processing unit,

the lethal pyrethroid is selected from one or two of beta-cypermethrin or cis-cypermethrin;

the knockdown pyrethroid is one or more selected from the group consisting of dextro-trans-cypermethrin, bifenthrin and permethrin.

4. A large particle size sanitary insecticidal suspension according to claim 1 or 2 wherein said wetting agent is selected from one or more of the group consisting of macromolecular block polyether wetting agents emulgen 3510, atlax 4894, ethyllan NS500LQ, ANTAROX BL-759.

5. A large particle size sanitary insecticidal suspension according to claim 1 or 2 wherein the dispersant is selected from the group consisting of phosphate esters and polycarboxylate salts, both in a weight ratio of 1:10 to 10:1; and, in addition, the processing unit,

the phosphate dispersant is one or more selected from Soprophor SC, SP-SC3060, dispersogen LFS and YUS-FS 3000;

the polycarboxylate dispersant is one or more selected from GEROON T/36, agrilan752, SP-2728 and GY-D06.

6. A large particle size sanitary insecticidal suspension according to claim 1 or 2 wherein said thickener is selected from one or both of xanthan gum and polyvinyl alcohol.

7. A large particle size sanitary insecticidal suspension according to claim 1 or 2, wherein,

the antifreezing agent is one or more selected from ethylene glycol, propylene glycol, glycerol and urea;

the defoamer is one or more selected from silicone oil, silicone compound, C10-20 saturated fatty acid and esters thereof, and C8-12 fatty alcohol defoamer;

8. A process for preparing a large particle size sanitary insecticidal suspension according to any one of claims 1 to 7, said process comprising the steps of:

9. The method for preparing a large particle size sanitary insecticidal suspension according to claim 8, wherein the temperature is controlled below 40 ℃ during the grinding process.

10. Use of a large particle size sanitary insecticidal suspension according to any one of claims 1 to 7 for the control of sanitary pests on surfaces.