WO2020093749A1 - Fungicidal composition containing terpenol and chitosan and preparation method therefor and use thereof - Google Patents

Abstract

Disclosed is a fungicidal composition containing terpenol and chitosan, which is comprised by the following active ingredients in parts by weight: 1-20 parts of terpenol and 1-5 parts of chitosan. The fungicidal composition further comprises 1-20 parts of levo-alpha-terpineol. The present invention has a relatively good synergistic effect by compounding both terpenol and chitosan, has an obvious synergistic effect by compounding levo-alpha-terpineol with terpenol and chitosan due to complementary functions, which can kill plant pathogenic fungi more effectively, and has a particularly good prevention and treatment effect on cucumber downy mildew, pearl plum anthracnose and mango powdery mildew.

Description

Fungicide composition containing terpene alcohol and chitosan, and preparation method and application thereof Technical field

The invention belongs to the technical field of pesticides, and particularly relates to a fungicide composition containing terpene alcohol and chitosan, and a preparation method and application thereof.

Background technique

Cucumber Downy Mildew Cucumber downy mildew, commonly known as "dried horse race" and "dry leaves", can be damaged at the seedling stage, mainly to the leaves and stems, and tendrils and pedicels are less affected. Cucumber downy mildew is the most common and most harmful disease in cucumber cultivation. The condition is violent, the disease is serious, and the spread is fast. If it is not controlled in time, it will cause devastating losses to the cucumber.

Longtan Pearl Plum is a late-ripening fine breed selected from local wild plums in Tian'e County, Guangxi. It was registered as a Geographical Indication of Agricultural Products by the Ministry of Agriculture in 2010. One of the leading industries in Exian. In recent years, the anthracnose disease of pearl plum has been serious. The disease harms young leaves, shoots and fruits, and causes serious losses to the production of pearl plum. At present, the local medicines used to control the anthracnose of pearl plum are relatively old, such as thiophanate-methyl, carbendazim, chlorothalonil, etc. These drugs are not ideal because of the resistance, which seriously restricts Longtan pearl plum Industry development.

Mango is one of the famous tropical fruits. It is loved by people. Mango fruit is rich in sugar, protein and crude fiber. The vitamin A precursors carotene and vitamin C in mango are particularly high and are rare in all fruits. Mango powdery mildew is mainly harmful to inflorescence and tender leaves. The main symptom is that some scattered white powdery plaques first appear on the injured organ, and then gradually expand and combine with each other to form a white powdery mold layer, and the tissue under the mold layer gradually becomes brown and necrotic. The damaging fungus belongs to the genus Aspergillus subsp. At present, the prevention and treatment effect on mango powdery mildew is not particularly ideal, the amount of medication is large, and the cure rate is low.

Terpineol (Terpineol, CAS No. 562-74-3) is an extract of Melaleuca alternifolia (Melaleuca alternifolia), a new type of botanical fungicide, which also has the function of biostimulant. As a biocide, it has protective and therapeutic effects and can prevent and control plant diseases caused by various fungi and bacteria. It has a good control effect on many diseases such as downy mildew, powdery mildew, early blight, late blight, leaf spot and other diseases on various crops. In addition to controlling fungal diseases, it can also control bacterial diseases caused by Xanthomonas and Pseudomonas. Safe and harmless to bees and other beneficial insects.

Chitosan (Chltosan), also known as chitin and chitin, is a water-soluble product produced by the removal of acetyl groups in concentrated alkali water. Its molecular formula is (C ₆ H ₁₁ O ₄ N) _n . Chitosan mainly inhibits the growth of pathogens by changing the structure and function of pathogen cell membranes, and has the effect of improving crop disease resistance and immune function. In agricultural production, chitosan is an excellent plant growth regulator and broad-spectrum fungicide. It is effective for the growth and reproduction of wheat Fusarium graminearum, rice bacterial leaf blight, potato ring rot fungus, cotton corner spot pathogen, etc. Fungal spore germination has obvious inhibitory effect.

L-alpha-terpineol (α- (L) -Terpineol) is a compound synthesized by Guangxi Zhuang Autonomous Region Research Institute of Chemical Industry (see Chinese patent, patent number: ZL03178548.4, authorized on December 26, 2007, the name : Preparation method of L-α-terpineol), which has good bactericidal activity, and also has good deodorizing, wetting and penetrating capabilities. The Guangxi Zhuang Autonomous Region Institute of Chemical Industry has conducted a lot of research on its biological activity, and the results show that the compound can be used as a pesticide fungicide or synergist.

With the implementation of the national pesticide and chemical fertilizer reduction policy and the large pollution and long-lasting residues of chemical agents, the development of environmentally friendly, efficient and low-toxic pesticides has become a hot topic. At present, there are no public reports on the research and application of the compounding of the three active ingredients, terpene alcohol, chitosan and L-terpineol.

Summary of the invention

The main object of the present invention is to provide a fungicidal composition containing terpene alcohol and chitosan, which has good bactericidal effect after being mixed with terpene alcohol, chitosan and L-alpha-terpineol, and increases The effect is obvious, especially in the application of pearl plum anthracnose.

To achieve the above objectives, the technical solution of the present invention is as follows:

The fungicidal composition containing terpene alcohol and chitosan of the present invention is composed of active ingredients including the following parts by weight: 1-20 parts of terpene alcohol and 1-5 parts of chitosan.

Further, it also includes the following parts by weight of active ingredients: L-alpha-terpineol 1-20 parts.

Further, the fungicidal composition containing terpene alcohol and chitosan is composed of the following parts by weight of active ingredients: 5-15 parts of terpene alcohol, 2-4 parts of chitosan, and L-alpha-pine 5-15 parts of oleyl alcohol.

Further, the fungicidal composition containing terpene alcohol and chitosan is combined with an auxiliary material to make a liquid preparation, characterized in that the auxiliary material includes: 1-70 parts by weight of solvent and 1-20 parts by weight Parts of surfactant, 0-2 parts by weight of defoamer, 1-5 parts by weight of antifreeze, 0-3 parts by weight of thickener.

Further, the solvent is one or more of methanol, ethanol, acetone, ethyl acetate, methyl oleate, cyclohexanone, propanol, solvent oil S100A, fatty acid methyl ester, diethylene glycol butyl ether mixture;

The surfactants are calcium dodecylbenzenesulfonate, phenethylphenol polyoxyethylene ether, triphenylethylphenol polyoxypropylene polyoxyethylene intercalation polymer, calcium lignosulfonate, alkylnaphthalene A mixture of one or more of sulfonate, fatty alcohol polyoxyethylene ether sulfate, polycarboxylate, polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene ether;

The defoamer is a mixture of one or more of silicone defoamer, phosphate defoamer, butyl phosphate, isobutyl phosphate, and higher alcohol;

The antifreeze is a mixture of one or more of ethylene glycol, propylene glycol, and glycerin;

The thickening agent is a mixture of one or more of xanthan gum, gum arabic, gelatin, polyvinyl alcohol, magnesium aluminum silicate, and sodium carboxymethyl cellulose.

Further, the fungicide composition containing terpene alcohol and chitosan is combined with an auxiliary material to make a solid preparation, characterized in that the auxiliary material includes: 10-70 parts by weight of an inert filler, 1-30 Parts by weight of functional accessories;

The functional auxiliary materials include one or more mixtures of surfactants, binders, and disintegrants.

Further, the inert filler is a mixture of one or more of attapulgite, diatomaceous earth, kaolin, white carbon, bentonite, light calcium carbonate, and talc;

The surfactant is calcium lignosulfonate, sodium p-hydroxyphenyl lignosulfonate, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, calcium dodecylbenzenesulfonate, alkyl Naphthalene sulfonate, sodium lignin sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lauryl ether sulfate, fatty alcohol polyoxyethylene ether sulfonate, polyether sodium sulfonate, phenethylphenol polyoxyethylene ether A mixture of one or more of

The binder is a mixture of one or more of starch, polyvinylpyrrolidone, carboxymethyl cellulose, carboxyethyl cellulose, gelatin, xanthan gum and gum arabic;

The disintegrant is a mixture of one or more of urea, sodium sulfate, calcium carbonate, ammonium sulfate, calcium sulfate, sodium chloride, magnesium chloride, and sodium bicarbonate.

Further, the preparation method of the solid preparation includes the following steps:

Mix each raw material with inert filler, pulverize it into a fine powder, add functional auxiliary materials, and mix evenly to make a powder; or on the basis of powder, add an appropriate amount of binder to further prepare granules.

The invention also provides the application of a fungicide composition containing terpene alcohol and chitosan in the prevention and treatment of cucumber downy mildew, pearl plum anthracnose and mango powdery mildew.

The present invention has the following significant effects:

1. The combination of terpene alcohol and chitosan has a good synergistic effect in itself, just as the experiments in Examples 21-22 fully proved the synergistic effect of these two components;

2. Due to its better dissolving, wetting and penetrating ability, L-alpha-terpineol can enhance the adhesion and absorption of terpene alcohols and chitosan on crops, thereby improving the action rate of these fungicides, It can reduce the dosage of pesticide formulations, thereby reducing costs; compound L-terpineol with terpene alcohol and chitosan to complement each other with obvious synergistic effect, which can more effectively kill plant pathogens, especially for Cucumber downy mildew, pearl plum anthracnose and mango powdery mildew have particularly good effects;

3. The present invention further mixes the synergist L-terpineol with terpene alcohol and chitosan, two compositions that themselves have a certain synergistic effect. The synergistic effect, as described in Example 23, can have a very large synergistic effect, can further reduce the dosage, and can be used in combination. The mechanism of action is completely different and will not produce cross-phase resistance;

4. The fungicide composition containing terpene alcohol and chitosan provided by the present invention also has better stability, improves the sterilization speed, and extends the shelf life. Terpene alcohol can affect the permeability barrier of the pathogenic cell membrane structure, destroying the cell membrane and cell wall, but the effect is slow; chitosan itself is a plant growth regulator that can induce crops to produce resistance factors and improve crop disease resistance; L-alpha-terpineol is used alone as a fungicide, with a large dosage and a short shelf life; after the combination of the three, the effect is good and the shelf life is long, which can effectively prevent and control plant diseases.

detailed description

The present invention is further illustrated by the following examples. It should be understood that the embodiments of the present invention are used to illustrate the present invention rather than limit the present invention. The simple improvements made to the present invention according to the essence of the present invention all fall within the scope of the claimed invention.

Example 1 (10% terpene alcohol, chitosan, L-alpha-terpineol microemulsion)

The raw material formula of this embodiment is:

Terpene alcohol 6%, chitosan 1%, L-alpha-terpineol 3%, N-methylpyrrolidone 8%, sodium dodecylbenzenesulfonate 6%, alkyl aryl polyoxypropylene polyoxy Vinyl ether 12%, propylene glycol 5%, the balance is water.

The preparation method of this embodiment is:

Terpene alcohol, L-α-terpineol, N-methylpyrrolidone, sodium dodecylbenzene sulfonate, alkylaryl polyoxypropylene polyoxyethylene ether, propylene glycol are fully stirred and dissolved in the container to prepare uniform Oil phase. Stir and mix chitosan and water in a container to prepare a uniform water phase. Then, the oil phase is slowly added to the water phase of the formula amount, and the mixture is stirred for 1 hour to obtain a composition microemulsion with an active ingredient content of 10%.

Example 2 (22% terpene alcohol, chitosan, levo-α-terpineol microemulsion)

The raw material formula of this embodiment is:

Terpene alcohol 10%, chitosan 2%, L-alpha-terpineol 10%, chloroform 14%, calcium dodecylbenzenesulfonate 5%, phenethylphenol polyoxyethylene ether 3%, fatty acid glycerin Ester 2%, ethylene glycol 2%, propylene glycol 1%, the balance is water.

The preparation method of this embodiment is:

Terpene alcohol, L-α-terpineol, calcium dodecylbenzenesulfonate, phenethylphenol polyoxyethylene ether, fatty acid glyceride, ethylene glycol, propylene glycol are fully stirred and dissolved in the container to prepare a uniform Oil phase. Stir and mix chitosan and water in a container to prepare a uniform water phase. Then, the oil phase was slowly added to the water phase of the formula amount, and the mixture was stirred for 1.5 hours to obtain a composition microemulsion with an active ingredient content of 17%.

Example 3 (20% terpene alcohol, chitosan, L-alpha-terpineol aqueous emulsion)

The raw material formula of this embodiment is:

Terpene alcohol 9%, chitosan 1%, L-alpha-terpineol 10%, calcium dodecylbenzenesulfonate 5%, dibenzyl biphenyl polyoxyethylene ether 10%, xylene 10% , Isooctyl alcohol 0.5%, ethylene glycol 1%, sorbitol 1%, polyvinyl alcohol 1%, the balance is water.

The preparation method of this embodiment is:

Xylene, terpene alcohol, L-alpha terpineol, calcium dodecylbenzenesulfonate, dibenzyl biphenyl polyoxyethylene ether, isooctyl alcohol, ethylene glycol, sorbitol, polyvinyl alcohol in this order Add to the reaction vessel, stir evenly and dissolve completely to get the oil phase. Stir and mix the chitosan and water in the vessel to prepare a uniform water phase. Under the condition of high shear in the homogenizer (rotation speed is 4000-5000r / min), slowly add the oil phase to the water phase. After the addition is completed, continue to maintain the above rotation speed and high shear for 30min to obtain the water emulsion of the herbicidal composition.

Example 4 (30% terpene alcohol, chitosan, l-alpha-terpineol wettable powder)

The raw material formula of this embodiment is:

Terpene alcohol 10%, chitosan 1%, L-alpha-terpineol 19%, fatty alcohol polyoxyethylene ether sulfonate 2%, calcium lignosulfonate 2%, calcium dodecylbenzenesulfonate 4%, the balance is white carbon black.

The preparation method of this embodiment is:

First, add white carbon black, terpene alcohol and L-alpha-terpineol to the blender and mix well, then add chitosan, fatty alcohol polyoxyethylene ether sulfonate, calcium lignosulfonate and dodecyl Sodium phenylsulfate was added to the mixer in order to mix thoroughly, and the mixed materials were added to the jet mill to pulverize to a fineness of 325 mesh to obtain a wettable powder of the composition with an active ingredient content of 30%.

Example 5 (40% terpene alcohol, chitosan, L-alpha-terpineol water dispersible granules)

The raw material formula of this embodiment is:

Terpene alcohol 20%, chitosan 2%, L-alpha-terpineol 18%, sodium lignin sulfonate 4%, alkanolamide polyoxyethylene ether sulfonate 2%, fatty alcohol polyoxyethylene ether sulfonate Sodium 2%, sulfate starch 10%, and the balance is bentonite.

The preparation method of this embodiment is:

First add bentonite, terpene alcohol and L-α-terpineol to the mixer and mix well, then add chitosan, sodium lignosulfonate, sodium alkanolamide polyoxyethylene ether sulfonate, fatty alcohol polyoxyethylene Sodium ether sulfonate is added to the mixer in order to be fully mixed. The mixed materials are added to the jet mill to be crushed to a fineness of 325 mesh. The crushed materials are then added to the mixer for 1 hour to form a certain concentration. Premix. Mix the sulfate starch and water in a weight ratio of 1: 2, and gelatinize them fully at 80 ℃. The premix and gelatinized sulfated starch are added to the extrusion granulator to make water-dispersible granules, and after drying, cooling, sieving and inspection, the finished product is packaged.

Example 6 (30% terpene alcohol, chitosan, L-alpha-terpineol dispersible oil suspension agent)

The raw material formula of this embodiment is:

Terpene alcohol 15%, chitosan 1%, L-alpha-terpineol 14%, alkyl naphthalene sulfonate formaldehyde condensate 5%, castor oil polyoxyethyl ether 4%, fatty alcohol polyoxyethyl Ether 8%, xanthan gum 1%, organic bentonite 1%, the balance is methyl oleate.

The preparation method of this embodiment is:

Add alkylnaphthalene sulfonate formaldehyde condensate, castor oil polyoxyethyl ether, fatty alcohol polyoxyethyl ether to methyl oleate, and mix well; the above system is added terpene alcohol, Chitosan and L-α-terpineol, and then add organic bentonite and xanthan gum to stir and mix; finally grind under the zirconium bead medium of the sand mill, and grind until the particle size is only 2 ~ 4μm. The composition having an active ingredient content of 30% can disperse oil suspending agents.

Example 7 (30% terpene alcohol, chitosan, L-alpha-terpineol aqueous emulsion)

The raw material formula of this embodiment is:

Terpene alcohol 8%, chitosan 2%, L-alpha terpineol 20%, calcium dodecylbenzenesulfonate 3%, phenethylphenol polyoxyethylene ether 3%, solvent oil S-100A5 %, The balance is water.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, first add chitosan to the water to dissolve to obtain the aqueous phase, then add terpene alcohol, L-alpha terpineol, calcium dodecylbenzenesulfonate, phenethylphenol Polyoxyethylene ether is added to S-100A and mixed to obtain an oil phase. Finally, the oil phase and the water phase are stirred and mixed evenly to prepare an aqueous emulsion.

Example 8 (29% terpene alcohol · chitosan · L-terpineol emulsifiable concentrate)

The raw material formula of this embodiment is:

Terpene alcohol 11%, chitosan 3%, L-alpha-terpineol 15%, calcium dodecylbenzenesulfonate 3%, phenethylphenol polyoxyethylene ether 3%, solvent oil S-100A7% , The balance is methanol.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, first dissolve the active ingredients in a solvent, then add L-terpineol and surfactant, stir and mix well to prepare an emulsifiable concentrate.

Example 9 (31% terpene alcohol, chitosan, L-alpha-terpineol wettable powder)

The raw material formula of this embodiment is:

Terpene alcohol 15%, chitosan 5%, L-alpha-terpineol 11%, methylenebisnaphthalene sulfonate 9%, phenethylphenol polyoxyethylene ether 5%, calcium sulfate 15%, more than The amount is white carbon black.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, mix, grind and pulverize the active ingredient and the inert ingredient, and then add functional auxiliary materials, mix evenly, and prepare a wettable powder.

Example 10 (26% terpene alcohol, chitosan, L-alpha-terpineol water dispersible granules)

The raw material formula of this embodiment is:

Terpene alcohol 18%, chitosan 1%, L-alpha-terpineol 7%, polyether sulfonate 5%, lignin sulfonate 10%, gelatin 4%, ammonium sulfate 6%, light carbonic acid 5% calcium, the balance is bentonite.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, mix, grind and pulverize the active ingredient of the pesticide and the inert ingredient, then add the functional auxiliary materials, and mix evenly to obtain a powder. The binder is added to the powder, and granulated by the screw to obtain water-dispersible granules.

Example 11 (11% terpene alcohol, chitosan, L-alpha-terpineol dispersible oil suspension agent)

The raw material formula of this embodiment is:

Terpene alcohol 7%, chitosan 3%, L-alpha-terpineol 1%, isobutyl phosphate 7%, fatty acid polyoxyethylene ether salt 4%, alkylphenol polyoxyethylene ether 5%, Gelatin 3%, ethylene glycol 4%, the balance is methyl oleate.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, mix them evenly, and grind them with a sand mill to prepare a dispersible oil suspension agent.

Example 12 (12% terpene alcohol · chitosan · L-α-terpineol aqueous emulsion)

The raw material formula of this embodiment is:

Terpene alcohol 5%, chitosan 2%, L-alpha-terpineol 5%, ethanol 2%, fatty acid methyl ester 30%, alkylphenol polyoxyethylene ether 6%, alkyl glycoside 2%, more than The amount is water.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, and then mix terpene alcohol, L-alpha terpineol, ethanol, fatty acid methyl ester, alkylphenol polyoxyethylene ether, alkyl glycoside to make oil phase, chitin The glycan is added to water to make an aqueous phase, and then under stirring conditions, the oil phase is added to the aqueous phase, and then put into a high-shear emulsifier for shearing to prepare an aqueous emulsion.

Example 13 (29% terpene alcohol, chitosan, levo-α-terpineol microemulsion)

The raw material formula of this embodiment is:

Terpene alcohol 9%, chitosan 3%, L-alpha terpineol 17%, sodium dodecylbenzenesulfonate 3%, alkylphenol polyoxyethylene ether 6%, cyclohexanone 9%, Acetone 7%, isopropyl alcohol 4%, ethylene glycol 4%, polyvinyl alcohol 2%, and the balance is water.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, and then mix the pesticide active ingredients, solvents, and surfactants to make the oil phase, add the other components to the water to make the water phase, and then add the oil to the water phase under stirring conditions Phase, then put into a high shear emulsifier, and the liquid obtained after shearing is filtered to obtain a microemulsion.

Example 14 (38% terpene alcohol, chitosan, L-alpha-terpineol water dispersible granules)

The raw material formula of this embodiment is:

Terpene alcohol 17%, chitosan 1%, L-alpha-terpineol 20%, calcium lignosulfonate 5%, polyoxyethylene sorbitan fatty acid ester 3%, sodium carboxyethyl cellulose 5% , Arabic gum 1%, starch 2%, magnesium chloride 3%, the balance is white carbon black.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, mix, grind and pulverize the active ingredient of the pesticide and the inert ingredient, then add the functional auxiliary materials, and mix evenly to obtain a powder. The binder is added to the powder, and granulated by the screw to obtain water-dispersible granules.

Example 15 (12% terpene alcohol, chitosan, levo-α-terpineol suspension agent)

The raw material formula of this embodiment is:

Terpene alcohol 8%, chitosan 2%, L-alpha-terpineol 2%, calcium lignosulfonate 2.5%, calcium dodecylbenzenesulfonate 2%, alkylphenol polyoxyethylene ether 4% , Silicone 0.02%, n-octanol 2%, ethylene glycol 4%, the balance is water.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, and prepare the suspending agent by ultrafine grinding method.

Example 16 (10% terpene alcohol · chitosan suspension agent)

The raw material formula of this embodiment is:

Terpene alcohol 7%, chitosan 3%, polyphosphate 7%, polycarboxylate 1%, polyoxyethylene sorbitan fatty acid ester 3%, gum arabic 0.08%, ethylene glycol 2%, excess The amount is water.

The preparation method of this embodiment is:

Add chitosan, polyphosphate, and polycarboxylate to the water and mix well; the above system is added terpene alcohol and polyoxyethylene sorbitan fatty acid ester in sequence under high-speed shear stirring, followed by acacia, ethylene The alcohol is stirred and mixed; finally, it is ground under the zirconium bead medium of the sand mill, and after examination, a composition suspending agent with an active ingredient content of 10% is obtained.

Example 17 (7% terpene alcohol · chitosan suspension agent)

The raw material formula of this embodiment is:

Terpene alcohol 5%, chitosan 2%, alkyl naphthalene sulfonate 5%, polycarboxylate 10%, xanthan gum 0.1%, propylene glycol 3%, the balance is water.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, mix well, sand, and pass the analysis to obtain the suspension agent.

Example 18 (12% terpene alcohol · chitosan wettable powder)

The raw material formula of this embodiment is:

Terpene alcohol 9%, chitosan 3%, p-hydroxyphenyl lignosulfonate 6%, phenethylphenol polyoxyethylene ether 5%, sodium chloride 4%, ammonium bicarbonate 3%, balance It is white carbon black.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, mix, grind and pulverize the active ingredient of the pesticide and the inert ingredient, and then add the functional auxiliary materials, mix evenly to prepare a wettable powder.

Example 19 (18% terpene alcohol · chitosan water dispersible granules)

The raw material formula of this embodiment is:

Terpene alcohol 17%, chitosan 1%, sodium lauryl sulfate 14%, sodium lauryl ether sulfate 2%, carboxyethyl cellulose 5%, urea 6%, magnesium sulfate 5%, the balance is Attapulgite.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, mix, grind and pulverize the active ingredient of the pesticide and the inert ingredient, then add the functional auxiliary materials, and mix evenly to obtain a powder. Then add the binder to the powder, granulate by screw, cut by cutter, and dry by hot air to prepare water-dispersible granules.

Example 20 (10% terpene alcohol · chitosan emulsifiable concentrate)

The raw material formula of this embodiment is:

Terpene alcohol 8%, chitosan 2%, calcium dodecylbenzenesulfonate 5%, phenethylphenol polyoxyethylene ether 9%, methanol 8%, acetone 9%, the balance is solvent oil S- 100A.

The preparation method of this embodiment is:

Weigh the above-mentioned components of the formula separately, first dissolve the active ingredient in the solvent, then add the surfactant, stir and mix evenly to prepare the emulsifiable concentrate.

Example 21 (Indoor virulence determination of cucumber downy mildew in different ratios of terpene alcohol, chitosan and L-terpineol)

Through the indoor bioassay, the synergistic situation after the compounding of terpene alcohol, chitosan and L-terpineol was clarified. The indoor bioassay test was conducted according to "NY / T1156.3-2006 Pesticide Indoor Bioassay Test Guideline Fungicide Part 3: Test Method for Inhibiting Cucumber Downy Mildew Pathogens", using cucumber downy mildew (Pseudoperonospora cubensis) as the test bacteria Collect fresh cucumber downy mildew leaves from Sitang Town, Nanning City, Guangxi Zhuang Autonomous Region, take them back to the laboratory, rinse the dust with clean water, keep them moisturized, and store them on the isolated leaves. Wash the sporangia on the back of the leaves with deionized water to prepare 1 × 105 ～ 1 × 107 sporangia / mL suspension for inoculation.

Dissolve terpene alcohol and L-terpineol with an appropriate amount of acetone, dissolve chitosan with an appropriate amount of water, and prepare a mother liquor with a mass concentration of 100 mg / L, and mix the three kinds of chemical solutions according to different mass ratios to obtain Mixtures of different proportions. Select 5 to 6 true leaf potted "Xintai Mithorn" cucumber plants, and spray the liquid medicine onto the plants with a sprayer until they are lost. The blank control was sprayed with clean water. Spray 3 plants per mass concentration. After the leaves are dried, cut 2 leaves with a uniform growth from each of the 3 plants treated for a total of 6 leaves; put the back of the leaves up in a Petri dish with wet filter paper, each leaf receives 4 drops of 10 μL The sporangia suspension was cultured in a light incubator at 18-20 ° C and 12h light / d for 7-10 days, and the diameter of the lesion was measured and recorded according to the control disease.

According to the survey data, the prevention and control effect is calculated according to the following formula:

In the formula:

P-prevention effect

D ₀ -diameter of blank control lesion

D ₁ -Diameter of the lesion treated by the agent

A linear regression analysis between the probability value of the control effect and the logarithm of the concentration was performed to obtain the regression equation of the toxicity of terpene alcohol, chitosan, L-terpineol and their mixtures to inhibit cucumber downy mildew infection of cucumber leaves Based on this, the EC50 values and correlation coefficients of terpene alcohols, chitosan, L-alpha-terpineol and their mixtures on cucumber downy mildew were determined.

According to Wadley (1967) formula, the synergistic effect of the blending of fungicides is calculated by the synergy of different agents:

In the formula: a, b, c represent terpene alcohol (A), chitosan (B), L-α-terpineol (C) the proportion of three agents in the mixture; EC50 (A), EC50 ( B), EC50 (C) represents the actual observed EC50 values of A, B, and C, EC50 (th) represents the theoretical EC50 value of the three agents A, B, and C mixed according to a: b: c, EC50 (ob) It is the actual observed EC50 value after mixing the three fungicides A, B and C according to a: b: c. SR> 1.5, synergism; SR <0.5, antagonism; SR between 0.5 and 1.5 indicates additive effect.

Table 1 Toxicity-enhancing effects of terpene alcohol, chitosan and L-terpineol on cucumber downy mildew

Mixture mix and ratio

Actual observation EC 50 value

Theoretical EC 50 value

Efficiency factor

A	(mg · L -1 )	(mg · L -1 )	(SR)
Terpene alcohol (a)	4.75	A	A
Chitosan (b)	18.45	A	A
L-α-terpineol (c)	90.23	A	A
a: b: c = 1: 1: 1	7.08	10.88	1.54
a: b: c = 10: 1: 1	3.55	5.53	1.56
a: b: c = 20: 1: 1	3.16	5.15	1.63
a: b: c = 30: 1: 1	4.27	5.01	1.17
a: b: c = 1: 5: 1	9.18	14.21	1.55
a: b: c = 1: 10: 1	15.29	15.71	1.03
a: b: c = 1: 1: 10	18.35	31.95	1.74
a: b: c = 1: 1: 20	26.82	45.23	1.69
a: b: c = 1: 1: 30	37.59	53.58	1.43

It can be seen from Table 1: the synergistic ratio range of terpene alcohol, chitosan, and L-alpha-terpineol to inhibit cucumber downy mildew infection of cucumber leaves is (1-20): (1-5): (1-20).

Example 22 (Field control effect of 20% terpene alcohol, chitosan, L-terpineol aqueous emulsion on Longtan pearl plum anthracnose)

(1) Test materials

20% terpene alcohol, chitosan, L-α-terpineol water emulsion (EW) (Guangxi Chemical Research Institute, mass ratio is 9: 1: 10); 9% terpene alcohol emulsion (EC) Kerton (Israel) Co., Ltd.]; 2% chitosan liquid (AS) (Shandong Keda Chuangye Biological Co., Ltd.); 20% L-alpha-terpineol emulsifiable concentrate (EC) (Guangxi Chemical Research Institute).

(2) Orchard situation

The experiment was conducted in Linlitun Pearl Plum Orchard, Suofa Village, Liupai Town, Tian'e County, Guangxi. The tested species was a 2-year-old Longtan Pearl Plum orchard, with plant spacing × row spacing = 3m × 5m, slope land, medium soil fertility, and basic fruit growth Similarly, anthracnose naturally occurs in orchards.

(3) Test design

The experiment set up 20% terpene alcohol · chitosan · L-alpha-terpineol EW60, 90, 120, 150g ai / hm ² , 9% terpene alcohol EC 150g ai / hm ² , 2% chitosan liquid AS 120g ai / hm ² , 20% L-α-terpineol EC800g ai / hm ² and clean water blank control, a total of 8 treatments, each treatment was repeated 4 times, each 3 plants was a cell, arranged in random blocks. Using the XQ-D-16 knapsack electric sprayer produced by Yingfan Sprayer Factory of Luqiao District, Taizhou City, the spray was evenly sprayed at the early stage of the new leaf disease, a total of 3 times, respectively, May 4, 2017, May 12, 2017 , May 19. No other fungicides were applied during the experiment. The management of fertilizer and water in orchards and the control of insect pests and weeds were consistent with local production.

(4) Drug effect investigation and statistics

The trial was conducted 4 times, and the pre-drug incidence base was investigated on May 3, 2017; the first, second, and third investigations after drug were on May 12, 19, and 26, 2017, respectively. Three plants in each community were investigated, and each plant was surveyed for 20 leaves according to the southeast, northwest, and 100 leaves for each plant, for a total of 300 leaves. Visually grade according to grading standards, record the total number of leaves and the number of diseased leaves at all levels, and calculate the average disease index and average prevention effect.

Disease leaf grading method: 0 level: no disease spots; 1 level: the area of disease spots accounts for less than 5% of the entire leaf area; 3 levels: the area of disease spots accounts for 6% to 15% of the entire leaf area; 5 levels: the area of disease spots It accounts for 16% to 25% of the entire leaf area; Grade 7: the lesion area accounts for 26% to 50% of the entire leaf area; Grade 9: lesion area accounts for more than 51% of the entire leaf area.

The differences in disease control effectiveness between treatments were statistically analyzed using Duncan ’s new double range method. Simultaneously conduct a visual inspection on the safety of the crops tested during the drug efficacy survey.

Formula for calculating efficacy:

(5) Results and analysis

It can be seen from Table 2 that the investigation results 8d (May 12) after the first application showed that 20% terpene alcohol, chitosan, L-alpha-terpineol EW 60, 90, 120, 150g ai / hm ² The average control effect of the treatment on the anthracnose of Longtan pearl plum was 37.82% ～ 56.75%, and there was no significant difference between the treatments and the control agents. 7d (May 19) after the second medicine, the prevention effect of 20% terpene alcohol · chitosan · L-α-terpineol EW 120g ai / hm ² was 80.43%, and 9% terpene alcohol EC The control effect (80.38%) is basically the same, better than that of 2% chitosan AS. After the third drug (May 26), the control effect of 20% terpene alcohol, chitosan, and L-alpha-terpineol EW under the treatment of 90g ai / hm ² on anthracnose of pearl plum and 9% terpene There was no significant difference in the control effect of alcohol EC. The control effects of the 120 and 150 g ai / hm ² treatments were 81.58% and 89.55%, respectively, which were significantly higher than those of other treatments.

Table 2 Control effect of 20% terpene alcohol, chitosan, L-alpha-terpineol EW on Longtan pearl plum anthracnose

Note: Different lowercase letters in the same column in the table indicate that the difference reaches a significant level (P <0.05), and different uppercase letters indicate that the difference reaches a very significant level (P <0.01).

Throughout the experiment, no phytotoxicity was found on the leaves of the treated plum tree.

(6) Summary and discussion

In the early stage of the disease, pesticides were applied to prevent and control Longtan pearl plum anthracnose. In the test, 20% terpene alcohol, chitosan, and L-alpha-terpineol had a good control effect, and the control effect increased with the increase of the concentration And improve. After the third application, the control effectiveness of 90% to 150g ai / hm ² of 20% terpene alcohol, chitosan, and L-alpha-terpineol reached 72.95 to 89.55%.

Example 23 (terpene alcohol, chitosan, L-alpha-terpineol compound on field control of mango powdery mildew)

Test method: The test was set up on the mango orchard of Guoliu Village, Dongjiang Town, Baise Field, Guangxi. Mango powdery mildew occurred all year round. The pesticide composition preparations of Examples 1-20 were used as the test agent. Butanan solution is a control agent, with 3 mango trees per area, arranged in random blocks, and repeated 4 times per treatment. Use XQ-D-16 knapsack-type electric sprayer to spray, start spraying when powdery mildew occurs sporadically, spray evenly, apply the first spray at the beginning of the disease, and apply the second spray 7 days later, and investigate the condition before spraying Base number, before and after the second application and 7 days after the second application, investigate the control effect. The test results are shown in Table 3:

Table 3 Field efficacy tests of different chemical treatments on mango powdery mildew

Test agent	Active ingredient dosage (g / hm 2 )	First prevention effect /%	Second prevention effect /%
Example 1	120	70.5	81.9
Example 2	120	71.6	82.6
Example 3	120	69.8	81.7
Example 4	120	74.3	88.5
Example 5	120	78.5	90.4
Example 6	120	75.4	89.6
Example 7	120	71.8	82.8
Example 8	120	69.5	80.7
Example 9	120	70.5	84.2
Example 10	120	72.5	88.6

Example 11	120	72.9	85.7
Example 12	120	69.1	83.5
Example 13	120	75.2	90.6
Example 14	120	74.6	88.1
Example 15	120	73.6	87.3
Example 16	120	67.3	80.6
Example 17	120	65.6	80.1
Example 18	120	70.1	83.4
Example 19	120	71.2	82.5
Example 20	120	70.5	81.4
9% terpene alcohol emulsifiable concentrate	150	63.8	78.2
2% chitosan liquid	120	31.5	44.8

The results of the field efficacy test are shown in Table 3. From Table 3, it can be seen that in Example 1-20, the combination of terpene alcohol and chitosan, and the pesticide formulation compounded with L-alpha-terpineol on mango powdery mildew The second control effect is more than 80%, which is significantly better than the control agent 9% terpene alcohol emulsifiable concentrate and 2% chitosan liquid. At the same ratio of terpene alcohol and chitosan, the treatment effects of Examples 11-15 with L-terpineol added were higher than those of Examples 16-20 without L-terpineol, indicating the addition L-alpha-terpineol can make the compound preparation of terpene alcohol and chitosan synergistic.

The bactericidal composition of the present invention has not been observed to cause phytotoxicity to mango crops within the scope of medication, indicating that the bactericidal composition of the present invention is also safer and worthy of popularization and application.

Claims (9)

1. A fungicide composition containing terpene alcohol and chitosan is characterized in that it is composed of the following active parts: 1-20 parts of terpene alcohol and 1-5 parts of chitosan.
2. The fungicide composition containing terpene alcohol and chitosan according to claim 1, further comprising the following parts by weight of active ingredient: 1-20 parts of L-terpineol.
3. The fungicidal composition containing terpene alcohol and chitosan according to claim 2, characterized in that it is composed of the following parts by weight of active ingredients: 5-15 parts of terpene alcohol and 2-4 of chitosan Parts, 5-15 parts of L-alpha-terpineol.
4. The fungicidal composition containing terpene alcohol and chitosan according to any one of claims 1 to 3, which is combined with an auxiliary material to make a liquid preparation, characterized in that the auxiliary material includes 1 to 70 parts by weight of Solvent, 1-20 parts by weight surfactant, 0-2 parts by weight defoamer, 1-5 parts by weight antifreeze, 0-3 parts by weight thickener.
5. The fungicide composition containing terpene alcohol and chitosan according to claim 4, characterized in that:

   The solvent is one or more mixtures of methanol, ethanol, acetone, ethyl acetate, methyl oleate, cyclohexanone, propanol, solvent oil S100A, fatty acid methyl ester, diethylene glycol butyl ether ;

   The surfactants are calcium dodecylbenzenesulfonate, phenethylphenol polyoxyethylene ether, triphenylethylphenol polyoxypropylene polyoxyethylene intercalation polymer, calcium lignosulfonate, alkylnaphthalene A mixture of one or more of sulfonate, fatty alcohol polyoxyethylene ether sulfate, polycarboxylate, polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene ether;

   The defoamer is a mixture of one or more of silicone defoamer, phosphate defoamer, butyl phosphate, isobutyl phosphate, and higher alcohol;

   The antifreeze is a mixture of one or more of ethylene glycol, propylene glycol, and glycerin;

   The thickening agent is a mixture of one or more of xanthan gum, gum arabic, gelatin, polyvinyl alcohol, magnesium aluminum silicate, and sodium carboxymethyl cellulose.
6. The fungicidal composition containing terpene alcohol and chitosan according to any one of claims 1 to 3, which is combined with an auxiliary material to form a solid preparation, characterized in that the auxiliary material includes 10-70 parts by weight of Inert filler, 1-30 parts by weight of functional auxiliary materials;

   The functional adjuvant includes one or more mixtures of surfactant, binder, and disintegrant.
7. The fungicide composition containing terpene alcohol and chitosan according to claim 6, characterized in that:

   The inert filler is a mixture of one or more of attapulgite, diatomaceous earth, kaolin, white carbon, bentonite, light calcium carbonate, and talc;

   The surfactant is calcium lignosulfonate, sodium p-hydroxyphenyl lignosulfonate, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, calcium dodecylbenzenesulfonate, alkyl Naphthalene sulfonate, sodium lignin sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lauryl ether sulfate, fatty alcohol polyoxyethylene ether sulfonate, polyether sodium sulfonate, phenethylphenol polyoxyethylene ether A mixture of one or more of

   The binder is a mixture of one or more of starch, polyvinylpyrrolidone, carboxymethyl cellulose, carboxyethyl cellulose, gelatin, xanthan gum and gum arabic;

   The disintegrant is a mixture of one or more of urea, sodium sulfate, calcium carbonate, ammonium sulfate, calcium sulfate, sodium chloride, magnesium chloride, and sodium bicarbonate.
8. The fungicidal composition containing terpene alcohol and chitosan according to claim 6, characterized in that the preparation method of the solid preparation comprises the following steps:

   Mix each raw material with inert filler, pulverize it into a fine powder, add functional auxiliary materials, and mix evenly to make a powder; or on the basis of powder, add an appropriate amount of binder to further prepare granules.
9. Use of the fungicidal composition containing terpene alcohol and chitosan as claimed in any one of claims 1 to 8 in controlling cucumber downy mildew, pearl plum anthracnose and mango powdery mildew.