CN102388914B - Combined synergistic agent for carbamide pesticide and environment-friendly pesticide containing same - Google Patents
Combined synergistic agent for carbamide pesticide and environment-friendly pesticide containing same Download PDFInfo
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- CN102388914B CN102388914B CN 201110315037 CN201110315037A CN102388914B CN 102388914 B CN102388914 B CN 102388914B CN 201110315037 CN201110315037 CN 201110315037 CN 201110315037 A CN201110315037 A CN 201110315037A CN 102388914 B CN102388914 B CN 102388914B
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Abstract
The invention discloses a combined synergistic agent for carbamide pesticides and an environment-friendly pesticide containing the same. The combined synergistic agent comprises salicylic acid and triphenyl phosphate; the laboratory test and the field test show that two types of carbamide pesticides have obvious synergistic effect through combining salicylic acid and triphenyl phosphate and then compounding with triflurnuron or hexaflumuron, so that the time of killing pests by triflurnuron can be shorted, the insecticidal activity of hexaflumuron is improved, pests can be prevented from damaging crops, and the usage amount of the pesticide can be reduced while the equivalent prevention effect is achieved; the synergistic effect of the combination of salicylic acid and triphenyl phosphate used as a synergistic agent on triflurnuron or hexaflumuron is remarkably better that of salicylic acid which is used as a synergistic agent individually and that of salicylic acid which is used as a synergistic agent individually, and the salicylic acid and triphenyl phosphate have a synergism effect.
Description
Technical field:
The present invention relates to a kind of pesticide synergistic agent and contain the agricultural chemicals of this synergist, be specifically related to a kind of compound synergist of carbamide pesticide and contain the environment-protection pesticide of this compound synergist.
Background technology:
Raising and science and technology development along with people's environmental consciousness, specificity agricultural chemicals such as insect growth regulator, IGR have obtained significant progress, wherein, using is chitin synthesis inhibitor more widely, this class action of agricultural chemicals is in the abnormal link of insect, can hinder the formation of the new epidermis of insect, suppress casting off a skin of insect and cause death the mechanism uniqueness.The following advantage of having compared with other chemical pesticide: 1) selectivity is strong, to people and animals and natural enemies security.2) little to eco-environmental impact.
A kind of chitin synthesis inhibitor agricultural chemicals that ureas is present output maximum, range of application is the widest, as killing bell urea (triflumuron), fluorine bell urea (hexaflumuron) etc., main synthetic by the chitin that influences insect, but this class agricultural insecticide speed is slower usually, also has the part insect to produce resistance simultaneously.The insecticidal effect that kills the bell urea is absolutely different with common insecticides, it is not direct kill insects, but grow by the normal growth that disturbs, destroys insect, the interference insect physiology course of casting off a skin, can suppress and destroy the formation of insect chitin synthetase, cause larva can not generate new epidermis, hinder its molt metamorphosis, insect is slowly caused death.It is slow to kill the effect of bell urea, and no systemic action has certain action of contace poison, and the lasting period is longer, holds to imitate to reach 30 days.But the major defect that kills the bell urea is that desinsection speed is slow, generally needs 4～7 days just can make the insect mortality.Because the defective of these aspects makes insecticide such as insect growth regulator, IGR be very limited in applying.
Under this background, seek the synergistic component of synergistic matter as this class agricultural chemicals, to improve the insecticidal toxicity of this class agricultural chemicals, shorten the death time of insect, thereby reach raising quick-acting, reduce insect density, the generation that reduces the pest damage degree and delay pest resistance to insecticide is as one of method of this class agricultural chemicals shortcoming problem of solution.And synergistic component is easily degraded at natural world, and is environmentally safe, is the principle of selective advance composition.Synergistic matter uses no insecticidal activity separately or has only extremely low insecticidal activity, can significantly improve the insecticidal activity of preparation in the time of in adding agricultural chemicals to.Yet insect growth adjusting at present waits the research and development of this class environment-protection pesticide synergist, is still a weak link in this insecticides application.
Salicylic acid is a kind of crystalline powdery thing of white, odorless, and the earlier little bitter back of flavor changes hot, extensively is present in the higher plant.Salicylic acid claims plant " antiphlogistic " again, and microorganism is had antibiotic property, is also bringing into play important physiological action in plant corpus, can not only regulate some growth and development processes of plant, also the plant antibiont coerce with abiotic stress in bringing into play important effect.Plant is after being subjected to virus, bacterial invasion, the salicylic acid level that is infected the position can significantly increase, the protect from infection diffusion at position of downright bad scab occurs, the salicylic acid content of non-infection site also can raise in addition, thereby makes it infect the generation resistance again to pathogen.Salicylic acid is important fine chemical material.In medical industry, salicylic acid itself is exactly the extremely wide disinfection preservative of a kind of purposes.Salicylic acid can dissolve the formation shape material (cement) between cutin, cuticula is produced come off, and is the medicine that is used for softening sclerderm or dissolving cutin, gathers blocked up cuticula so can remove, and enhances metabolism.Salicylic acid has outstanding exfoliating, unclogging ability.Salicylic acid is used aspect medical many, be widely used in the skin disease and cosmetics in, then be applied to bactericide synergy in the agricultural chemicals.
Triphenyl phosphate is a kind of white, odorless crystalline powder, and little have a hygroscopy.Be mainly used in chemical products, as nitrocellulose, the flame-retardant plasticizer of cellulose acetate film, the plasticizer of polyvinyl chloride, the camphor noninflammability substitute in the viscose rayon.Triphenyl phosphate has the effect that suppresses the insect bodies endoenzyme.And many results of study show, insect metabolic resistance mechanism mainly is because due to various detoxification enzyme activities increase.Using synergist and have the metabolism selective advantage of these enzymes in order to eliminate insect colony, is to overcome and delay one of approach of pest resistance development.
Summary of the invention:
First purpose of the present invention provide a kind of effective promotion carbamide pesticide to larval phase insect insecticidal activity and the compound synergist of the carbamide pesticide of safety and environmental protection.
The compound synergist of carbamide pesticide of the present invention is made up of salicylic acid and triphenyl phosphate.
The compound synergist of described carbamide pesticide preferably is made up of by mass ratio 3: 0.1～150 salicylic acid and triphenyl phosphate, is to be made up of at 2: 3 salicylic acid and triphenyl phosphate by mass ratio preferably further.
Find through experiment, when using salicylic acid or triphenyl phosphate to be used to prevent and treat lepidopterous larvae and straw mushroom nematode separately, almost there is not insecticidal action, but salicylic acid or triphenyl phosphate and carbamide pesticide mix when using, then the latter there is obvious synergistic effect, can increase lethality and shorten the death time, it is significant to the insecticide of delayed action particularly can to shorten the death time, also can reduce the utilization of pesticides amount simultaneously.The present invention also further finds through laboratory test and field trial, by the combination of salicylic acid and triphenyl phosphate with after bell urea or fluorine bell urea mix extremely, synergistic effect to two kinds of urea insecticides is remarkable, can shorten and kill the lethal time of bell urea insect, with the insecticidal activity that improves fluorine bell urea, prevent that insect from continuing damage to crops, under equal preventive effect, can reduce the utilization of pesticides amount.Salicylic acid and triphenyl phosphate combination use salicylic acid or triphenyl phosphate as synergist as synergist separately to the synergistic effect ratio that kills bell urea or fluorine bell urea, and its synergistic effect is more obvious, has synergistic effect between salicylic acid and the triphenyl phosphate.
Therefore, second purpose of the present invention composition of providing salicylic acid and triphenyl phosphate is as the application in the carbamide pesticide synergist.
The 3rd purpose of the present invention provides a kind of environment-protection pesticide that contains compound synergist, comprises carbamide pesticide and auxiliary agent, it is characterized in that also comprise compound synergist, this compound synergist is made up of salicylic acid and triphenyl phosphate.
Described compound synergist is 3: 0.1～150 to be made up of salicylic acid and triphenyl phosphate by mass ratio preferably, is to be made up of at 2: 3 salicylic acid and triphenyl phosphate by mass ratio preferably further.
Preferably, the mass ratio of described compound synergist and carbamide pesticide is 1: 0.1～80.
Described carbamide pesticide is preferably and kills bell urea or fluorine bell urea.
The described environment-protection pesticide that contains compound synergist is preferably, and by gross mass mark 100%, comprises bell urea 5～40% extremely; Salicylic acid 0.5～15%; Triphenyl phosphate 0.5～25%; All the other are auxiliary agent.
The described environment-protection pesticide that contains compound synergist is preferably, and by gross mass mark 100%, comprises fluorine bell urea 5～30%; Salicylic acid 0.5～15%; Triphenyl phosphate 0.5～25%; All the other are auxiliary agent.
Described auxiliary agent comprises emulsifier, solvent, cosolvent and filler.Emulsifier can be by calcium dodecyl benzene sulfonate (agricultural newborn 500#), styryl phenol formaldehyde resin polyoxyethylene polyoxypropylene block type polyethers (agricultural newborn 34#), alkylphenol polyoxyethylene (NP-10, OP-10 and OP-15), this coils 20-40 (S-20 and S-40), styrene (or a-methyl styrene) phenol formaldehyde resin polyoxyethylene (Nongru-700 #), dibenzyl xenyl APEO (agricultural newborn 300#), styryl phenol polyvinylether (agricultural newborn 603#), polyoxyethylene nonylphenol ether modified phosphate fat (phosphoric acid fat 500#), one or more compositions wherein such as Tea Saponin.Solvent can be made up of wherein one or more such as acetone, dimethyl formamide, cyclohexanone, S-150, N-alkyl pyrrolidone.Cosolvent can be made up of wherein one or more such as ethylene glycol phenyl ether, n-butanol, ethylene glycol, propane diols, methyl alcohol.One or more compositions wherein such as the optional diatomite of filler, kaolin, potter's clay, calcium carbonate, white carbon, water.Those skilled in the art are the formulation of agricultural chemicals as required, as formulations such as missible oil or suspending agents, prepares according to the conventional knowledge adding corresponding adjuvants of this area.
Carbamide pesticide compound synergist of the present invention can spray with carbamide pesticide independent water-soluble back, also can directly add and make various formulations in the carbamide pesticide.
Compared with prior art, the present invention has following characteristics:
1. compound synergist provided by the present invention is with respect to single synergistic component salicylic acid or triphenyl phosphate and kill the bell urea and fluorine bell urea is mixed, toxicity test to the straw mushroom nematode shows as synergistic function, and its co-toxicity coefficient of composite dose (CTC) is 129.79 and 130.95.Salicylic acid produces the reaction of casting off a skin, and triphenyl phosphate suppresses the enzyme in the insect bodies.Both synergy mechanism differences, the combination Synergistic can enlarge the synergy scope, shortens the insect death time, improves the control efficiency of resistant insect.
2. bell urea extremely, the fluorine bell urea that contains compound synergist provided by the present invention distinguished high 1.58～4.16 times and 1.47～1.83 times to the quick-acting of the insecticidal toxicity of beet armyworm and diamond-back moth than its independent use.Therefore compound synergist provided by the present invention can promote the insecticidal effect of insecticide effectively, improves drug effect, can reduce the consumption of insecticide under equal preventive effect.
3. compound synergist salicylic acid provided by the present invention and triphenyl phosphate are industrial chemicals, wide material sources.During as the synergistic component of insecticide, easily degraded, noresidue, the pesticide synergistic agent that is suitable as a kind of environmental protection is promoted the use of.
4. compound synergist used in the present invention can delay insect to the drug-fast generation of insecticide, and is significant for the use of applying environment-friendly pesticide, the medication of minimizing high residue chemistry.
5. preparation method of the present invention is simple, raw material sources are extensive, with low cost.
Embodiment:
Following examples are to further specify of the present invention, rather than limitation of the present invention.
Embodiment 1: the bell urea missible oil extremely that contains compound synergist
By gross mass mark 100%, comprise insecticide: kill bell urea 5%, synergist: salicylic acid 0.5%, synergist: triphenyl phosphate 0.8%, emulsifier: alkylphenol polyoxyethylene (NP-10) 5%, cosolvent: ethylene glycol 5%, solvent: dimethyl formamide is supplemented to 100%.Compound method: insecticide, synergist, emulsifier, cosolvent, solvent are put into mixer successively, stirred 30 minutes, treat can finished product behind the missible oil clear.
Embodiment 2: the bell urea suspending agent extremely that contains compound synergist
By gross mass mark 100%, comprise insecticide: kill bell urea 20%, synergist: salicylic acid 0.5%, synergist: triphenyl phosphate 25%, emulsifier: Tea Saponin 10%, solvent: cyclohexanone 15%, cosolvent: ethylene glycol 5%, filler: white carbon 1%, water supplies 100%.Compound method: insecticide, synergist, emulsifier, cosolvent, solvent, suitable quantity of water are put into reactor successively, carried out emulsification pretreatment 30 minutes with high-speed shearing machine.Add filler then, water supplies 100%, carries out high speed shear emulsification 1 hour again, treat to filter out sediment, the can finished product after suspending agent is evenly.
Embodiment 3: the bell urea suspending agent extremely that contains compound synergist
By gross mass mark 100%, comprise insecticide: kill bell urea 40%, synergist: salicylic acid 15%, synergist: triphenyl phosphate 0.5%, emulsifier: Tea Saponin 15%, solvent: cyclohexanone 15%, cosolvent: ethylene glycol 5%, filler: white carbon 0.5%, water supplies 100%.Compound method: insecticide, synergist, emulsifier, cosolvent, solvent, suitable quantity of water are put into reactor successively, carried out emulsification pretreatment 30 minutes with high-speed shearing machine.Add filler then, water supplies 100%, carries out high speed shear emulsification 1 hour again, treat to filter out sediment, the can finished product after suspending agent is evenly.
Embodiment 4: the 5 percent of hexaflumuron emulsifiable concentrate that contains compound synergist
By gross mass mark 100%, comprise insecticide: fluorine bell urea 5%, synergist: salicylic acid 0.5%, synergist: triphenyl phosphate 25%, styryl phenol polyvinylether (agricultural newborn 603#) 10%, cosolvent: ethylene glycol 5%, solvent: dimethyl formamide is supplemented to 100%.Compound method: insecticide, synergist, emulsifier, cosolvent, solvent are put into mixer successively, stirred 30 minutes, treat can finished product behind the missible oil clear.
Embodiment 5: the fluorine bell urea suspending agent that contains compound synergist
By gross mass mark 100%, comprise insecticide: fluorine bell urea 30%, synergist: salicylic acid 15%, synergist: triphenyl phosphate 0.5%, emulsifier: Tea Saponin 15%, solvent: cyclohexanone 15%, cosolvent: ethylene glycol 5%, filler: white carbon 0.5%, water supplies 100%.Compound method: insecticide, synergist, emulsifier, cosolvent, solvent, suitable quantity of water are put into reactor successively, carried out emulsification pretreatment 30 minutes with high-speed shearing machine.Add filler then, water supplies 100%, carries out high speed shear emulsification 1 hour again, treat to filter out sediment, the can finished product after suspending agent is evenly.
Embodiment 6: have synergistic action effect to killing the bell urea between salicylic acid and the triphenyl phosphate in the compound synergist of the present invention:
With 5g kill bell urea standard items, the 12g triphenyl phosphate mixes, and adds alkylphenol polyoxyethylene (NP-10) 5g again, ethylene glycol 5g, dimethyl formamide is supplemented to 100%, the content that make to kill the bell urea is 5% (mass fraction).
With 5g kill bell urea standard items, the 8g salicylic acid mixes, and adds alkylphenol polyoxyethylene (NP-10) 5g again, ethylene glycol 5g, dimethyl formamide is supplemented to 100%, the content that make to kill the bell urea is 5% (mass fraction).
5g is killed bell urea standard items, 6g triphenyl phosphate, 4g salicylic acid mix, add alkylphenol polyoxyethylene (NP-10) 5g again, ethylene glycol 5g, dimethyl formamide is supplemented to 100%, makes that the content that kills the bell urea is 5% (mass fraction).
Compound method: insecticide, synergist, emulsifier, cosolvent, solvent are put into mixer successively, stirred 30 minutes, treat can finished product behind the missible oil clear.
Water is 1000 times of its dilutions during use, carries out straw mushroom nematoda control test indoor.Kill 1000 times of liquid of bell urea with commodity 5% simultaneously and do contrast, other one group is blank.At test under microscope, statistics.According to survey data, analyze with statistical analysis system (SAS), data handling system softwares such as (DPS), calculate the LT of each medicament
50, and calculating co-toxicity coefficient (CTC) value of mixture according to the abundant method of Sun Yun, its result is as shown in table 1.
Table 1: have synergistic action effect to killing the bell urea between salicylic acid and the triphenyl phosphate in the compound synergist of the present invention
Annotate: composite dose co-toxicity coefficient (CTC) 〉=120 shows as synergistic effect; CTC≤80 show as antagonism; 80＜CTC＜120 show as summation action.A:5% kills bell urea+12% triphenyl phosphate; B:5% kills bell urea+8% salicylic acid; A+B:5% kills bell urea+6% triphenyl phosphate+4% salicylic acid
As can be seen from Table 1, the synergist that is mixed of salicylic acid and triphenyl phosphate is CTC=129.79 with respect to the co-toxicity coefficient of single synergist, greater than 120, show as synergistic effect, illustrate to have synergistic effect between salicylic acid and the triphenyl phosphate, both combinations have synergistic effect to killing the bell urea.
Embodiment 7: between salicylic acid and the triphenyl phosphate fluorine bell urea is had synergistic action effect in the compound synergist of the present invention:
5g fluorine bell urea standard items, 12g triphenyl phosphate are mixed, add alkylphenol polyoxyethylene (NP-10) 5g again, ethylene glycol 5g, dimethyl formamide is supplemented to 100%, makes that the content of fluorine bell urea is 5% (mass fraction).
5g fluorine bell urea standard items, 8g salicylic acid are mixed, add alkylphenol polyoxyethylene (NP-10) 5g again, ethylene glycol 5g, dimethyl formamide is supplemented to 100%, makes that the content of fluorine bell urea is 5% (mass fraction).
5g fluorine bell urea standard items, 6g triphenyl phosphate, 4g salicylic acid are mixed, add alkylphenol polyoxyethylene (NP-10) 5g again, ethylene glycol 5g, dimethyl formamide is supplemented to 100%, makes that the content of fluorine bell urea is 5% (mass fraction).
Compound method: insecticide, synergist, emulsifier, cosolvent, solvent are put into mixer successively, stirred 30 minutes, treat can finished product behind the missible oil clear.
Water is 1000 times of its dilutions during use, carries out straw mushroom nematoda control test indoor.Simultaneously do contrast with 1000 times of liquid of commodity 5% fluorine bell urea, other one group is blank.At test under microscope, statistics.According to survey data, analyze with statistical analysis system (SAS), data handling system softwares such as (DPS), calculate the LT of each medicament
50, and calculating co-toxicity coefficient (CTC) value of mixture according to the abundant method of Sun Yun, its result is as shown in table 2.
Table 2: between salicylic acid and the triphenyl phosphate fluorine bell urea is had synergistic action effect in the compound synergist of the present invention
Annotate: composite dose co-toxicity coefficient (CTC) 〉=120 shows as synergistic effect; CTC≤80 show as antagonism; 80＜CTC＜120 show as summation action.A:5% fluorine bell urea+12% triphenyl phosphate; B:5% fluorine bell urea+8% salicylic acid; A+B:5% fluorine bell urea+6% triphenyl phosphate+4% salicylic acid
As can be seen from Table 2, the synergist that is mixed of salicylic acid and triphenyl phosphate is CTC=130.95 with respect to the co-toxicity coefficient of single synergist, greater than 120, show as synergistic effect, illustrate to have synergistic effect between salicylic acid and the triphenyl phosphate, both combinations have synergistic effect to fluorine bell urea.
Embodiment 8: insecticide of the present invention is to the indoor pharmacodynamic test of straw mushroom nematode
Get bell urea standard items sample 5g extremely, salicylic acid 4g, triphenyl phosphate 6g, mix, add auxiliary agent, be made into 5% (mass fraction) that contains compound synergist and kill bell urea (compound method is with embodiment 6), use this prescription with 1000 times of liquid of its dilution, carry out straw mushroom nematoda control test indoor.Simultaneously with commodity 5% kill 1000 times of liquid of bell urea, 3000 times of liquid of 1.8% abamectin emulsifiable concentrate are done contrast, other one group is blank.At test under microscope, statistics.Control efficiency sees Table 3.Wherein computing formula is as follows:
Table 3: insecticide of the present invention and other insecticide are to the comparison of straw mushroom nematoda control effect
As can be seen from Table 3, add 5% of compound synergist and kill the bell urea and not only shortened and kill the lethal time of bell urea, also improved the control efficiency of killing the bell urea insect.
Embodiment 9: insecticide of the present invention is to the field control effect of beet armyworm
Get extremely bell urea standard items sample 5g, salicylic acid 4g, triphenyl phosphate 6g mixes, and adds auxiliary agent, is made into to contain 5% of compound synergist and kill bell urea (compound method is with embodiment 6), with 1500 times of liquid of its dilution, carries out beet armyworm control test in the field.Simultaneously with commodity 5% kill 1500 times of liquid of bell urea, 2000 times of liquid of 1.8% abamectin emulsifiable concentrate are done contrast, other one group is blank.Control efficiency sees Table 4.
Table 4: insecticide of the present invention and other insecticide are to the comparison of beet armyworm control efficiency
As can be seen from Table 4, add 5% of compound synergist and kill the bell urea and not only shortened and kill the lethal time of bell urea to insect, also improved the control efficiency of killing the bell urea, to kill the bell urea high 1.58～4.16 times than using separately for quick-acting.
Embodiment 10: insecticide of the present invention is to the field control effect of diamond-back moth
Get fluorine bell urea standard items sample 5g, salicylic acid 4g, triphenyl phosphate 6g, add auxiliary agent, mix, be made into the 5% fluorine bell urea (compound method is with embodiment 6) that contains compound synergist, use this prescription,, carry out diamond-back moth control test in the field 1500 times of liquid of its dilution.Simultaneously do contrast with 1500 times of liquid of commodity 5% fluorine bell urea, 2000 times of liquid of 1.8% abamectin emulsifiable concentrate, other one group is blank.Control efficiency sees Table 5.
Table 5: insecticide of the present invention and other insecticide are to the comparison of diamond-back moth control efficiency
As can be seen from Table 5, the 5% fluorine bell urea that adds compound synergist has not only shortened the lethal time of fluorine bell urea to insect, has also improved the control efficiency of fluorine bell urea.Quick-acting is higher 1.47～1.83 times than using fluorine bell urea separately.
Embodiment 11:
Compound synergist: salicylic acid: triphenyl phosphate=4: 6 (mass ratio), insecticide: kill the bell urea, its amount sees Table 6 with the relation (mass ratio) of synergist.
According to conventional method insecticide, synergist, emulsifier, cosolvent, solvent are put into mixer successively, stirred 30 minutes, treat the agricultural chemicals of can finished product missible oil formulation behind the missible oil clear.
Above-mentioned agricultural chemicals is carried out indoor cabbage caterpillar test, and its result of the test is as shown in table 6:
Table 6:
| Proportioning (is killed the bell urea: compound synergist) | Regression equation | Correlation coefficient (r) | LC 50(ppm) | SR | SD |
| y＝3.4172+1.0305x | 0.9563 | 34.35 | |||
| 2∶1 | y＝3.4972+1.0422x | 0.9499 | 27.66 | 1.24 | 6.69 |
| 1∶1 | y＝3.6330+1.0532x | 0.9468 | 19.86 | 1.73 | 14.49 |
| 1∶2 | y＝3.8588+1.1616x | 0.9842 | 9.60 | 3.58 | 24.75 |
| 1∶3 | y＝3.7703+1.2968x | 0.9899 | 8.88 | 3.87 | 25.48 |
| 1∶4 | y＝3.8463+1.2219x | 0.9918 | 8.79 | 3.91 | 25.56 |
As can be seen from Table 6, synergist is many more, and effect is good more.According to trend is that synergist is The more the better, but synergist many have a poisoning, field trial shows, when salicylic acid content reached 20% in the synergist, 1000 times were sprayed tender dish leaves and have poisoning and take place.
Claims (3)
1. a compound synergist that kills bell urea or fluorine bell urea is characterized in that, is made up of by mass ratio 2:3 salicylic acid and triphenyl phosphate.
2. salicylic acid and triphenyl phosphate are pressed composition that mass ratio 2:3 forms as the application of killing in bell urea or the fluorine bell urea synergist.
3. an environment-protection pesticide that contains compound synergist is characterized in that, by gross mass mark 100%, comprises and kills bell urea or fluorine bell urea 5%; Salicylic acid 4%; Triphenyl phosphate 6%; All the other are auxiliary agent.
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