KR100463120B1 - Emission-controlled insecticide composition - Google Patents

Abstract

The present invention relates to controlled release insect repellent devices and methods for repelling insects from food, tobacco or other consumables. The controlled release insect repellent device of the present invention comprises a repellent composition in contact with a substrate. The controlled release insect repellent device of the present invention is prepared by a method comprising applying a repellent composition to a substrate, wherein the repellent compound used is present in the controlled release repellent device in an amount that is nontoxic to humans and animals upon release. . The method of insect repelling by the present invention includes placing a controlled release insect repellent device in an area where insects may be present. The insect repellent composition comprises a repellent agent, optionally with a solvent, that is a repellent compound and a compound that may be a synthetic and / or natural material. The insect repellent compound can be selected from the group consisting of essential oils and the active ingredients of the essential oils.

Description

Controlled release insect repellent composition

The present invention relates to a controlled-release insect repellent device of an insect repellent compound, and a method of insect repellent from food, tobacco or other consumables using the controlled release insect repellent device. The controlled release insect repellent device of the present invention is safe for contact with consumables and can be used in any area where insects need to be blocked. The controlled release insect repellent device of the present invention is also environmentally safe.

Compounds that kill insects are known, but are often unpleasant in contact with the human body. Many compounds have been found to be toxic to humans and the environment and therefore cannot be placed in direct or indirect contact with food, tobacco or other consumables. In addition, it may take several years for FDA and EPA to approve new compounds for pest control.

It is an object of the present invention to provide a controlled release insect repellent device which is effective for insect repelling, comfortable to most people upon contact, and which does not have a harmful effect on the environment. Many of the insect repellent compounds that can be used in the controlled release insect repellent devices of the present invention are those already approved for food and medical use.

The present invention provides an environmentally friendly controlled release insect repellent device for insect repellent from food, tobacco or other consumables, wherein the device of the present invention is safe for use in foods, including infant foods, and is safe for humans, animals or the environment. It is not harmful. The present invention also provides a method of insect repellent from food, tobacco or other consumables using the controlled release insect repellent device. The controlled release insect repellent device of the present invention comprises a repellent composition in contact with a substrate. Controlled release insect repellent devices are manufactured by a method that includes attaching the insect repellent composition to a substrate. Insect control methods include placing a controlled release insect repellent device in an area where insects may be present. The insect repellent composition used in the controlled release insect repellent device is prepared by mixing the insect repellent compound, the release controlling agent and optionally a solvent to form a composition precursor, which is then applied to a substrate and dried as necessary to form the insect repellent composition. Other additives such as coupling agents, release rate control agents and thickeners may also be used. The insect repellent compound may be selected from the group consisting of essential oils and the active ingredients of the essential oils. Essential oils are defined as any class of volatile oils obtained from plants and retaining the fragrance and other properties of the plant. Release control agents include compounds that can be synthetic and / or natural materials.

The controlled release insect repellent device of the present invention contains only a small amount of the active ingredient in the insect repellent composition, the active ingredient is safe for use in food, tobacco or other consumables, and is comfortable for most people who come into contact with the vapor of the active ingredient. Because it is advantageous. In addition, the controlled release insect repellent device of the present invention remains active for a predetermined period of time, which may vary from a short time to a long time. The active ingredient is present in the controlled release insect repellent device in an amount that is nontoxic to humans and animals upon release from the device.

Advantages of the present invention can be clearly understood from the following detailed description and the accompanying drawings.

The environmentally friendly controlled release insect repellent device of the present invention contemplates the release control of the insect repellent, which remains useful for a predetermined period of time, and is safer and healthier for use in products to which adults, children and animals come in contact. Provides an insect repellent device. In addition, the device of the present invention provides an insect repellent effect without any odor detected by the human body.

The present invention teaches that the rate of vapor release of a compound having the ability to repel insects can be adjusted by the addition of a release controlling agent. The mixing of the insect repellent compound with the release controlling agent in which the active ingredient in the insect repellent compound may be mixed may permit control of the release of the vapor of the active ingredient in some cases due to the affinity of the release controlling agent for the active ingredient. have. Changes in the relative proportions of the insect repellent compound and release control agent in the insect repellent composition and the selection of concentrations, amounts and types of active substances (e.g., essential oils) and inactive substances (e.g., release control agents) allow for more granular control of release rates will be. In addition, the mixing of the insect repellent compound with the additive also contributes to this release control. The ability to control the release rate is an advantage of the release controlled insect repellent device. Control of the release rate extends its useful life by extending the duration of the efficacy of the insect repellent. Control of the release rate also prevents the insect repellent compound from being overexposed to an article that comes into contact with or is adjacent to the device.

The controlled release insect repellent device has another advantage in that it can be used to repel insects from food, tobacco or other consumables and can be used in direct or indirect contact with the consumables. The device may also be used for non-consumables, ie textiles and furs. The insect repellent compound, when released, is present in an amount that is nontoxic to adults, children, and animals. Controlling the release rate of the insecticide compound when the controlled release insect repellent device comes into contact with the consumable can control insects without releasing unpleasant odors or changing the taste of the consumable, which is an undesirable problem for consumer goods.

The insect repellent composition of the present invention is prepared by mixing the repellent compound and the release controlling agent, optionally with a solvent and / or other additives to form a mixture precursor, and then applying the mixture precursor to the substrate. The mixture precursor is then dried as needed to form a repellent composition on the substrate. The pH of the mixture precursors that can be used is limited only by the effect on the substrate and coating. The mixture precursor is preferably applied to a substrate and then dried. Drying temperatures are considered insignificant, but the usable temperature range is from about -17 ° C to about 315 ° C, preferably from about 37 ° C to about 205 ° C, most preferably from about 37 ° C to about 150 ° C.

Examples of insect repellent compounds include essential oils such as almond bitter oil, anise oil, basil oil, caraway oil, soybean oil, cedar leaf oil, celery oil, Chamomile oil, cinnamon oil, citronella oil, clove oil, coriander oil, cumin oil, inill oil, eucalyptus oil, fennel oil, ginger oil, Grapefruit oil, lemon oil, lime oil, mint oil, parsley oil, pepper oil, rose oil, spearmint oil (menthol), sweet orange oil, thyme oil, turmeric oil, and wintergreen oil (Also known as bone teria oil). Examples of active ingredients in essential oils include cytonelal, methyl salicylate, ethyl salicylate, propyl salicylate, cytonelol, saprolol and D-limonene. Preferred insect repellent compounds are pressurized oil, which is essential oil, or methyl salicylate, an active ingredient thereof.

The concentration of the insect repellent compound in the insect repellent composition after the insect repellent composition is applied and dried on the substrate is about 0.1% to about 80% by weight, preferably about 0.1% to about 40% by weight, and most preferably about 0.1% by weight. To about 20% by weight (dry weight), with the remainder of the insect repellent composition being a release agent, a solvent, and / or other additives that do not evaporate during the drying step.

Release control agents include compounds that can control the rate of release of the insect repellent compound from the device. Any compound approved for use in direct or indirect contact with food, tobacco or other consumables may be used as the release agent. Examples of release controlling agents include inorganic and organic polymers including, for example, natural, synthetic and semisynthetic organic polymers. Examples of such polymers include latex resins (e.g. styrene acrylic resins and styrene butadiene resins), solution acrylics, polyvinyl resins, sodium alginate, natural gums or hydrocolloids (e.g. gum arabic, sodium alginate, guar) Pectin), synthetic gums (e.g. fumigated resins), polyethylene waxes, wax emulsions, polymer printing inks (e.g. special prescriptions such as UV and electron beams), polymeric aqueous foams, adhesives (e.g., low temperature curable adhesives, hot melt adhesives) , Printable heat curable and ultrasonic adhesives, and reactive and non-reactive types of laminating adhesives), polymeric protective coatings, primers and micelles of natural resin formulations (e.g. copal, zien and proteins). Can be. Examples of non-polymeric release agents that can be used include non-polymeric printing inks, non-polymeric aqueous foams, non-polymeric protective coatings, and fillers such as sawdust, clays and zeolites. Although not listed, other compounds are also contemplated that may allow control of the release rate of the insecticide compound from the device.

Release control agents may also optionally include additives such as solvents and / or coupling agents or dispersants such as 2-amino-2-methyl-1-propanol. Solvents that can be used are those that are compatible with the insecticide compound and the release controlling agent used to form the mixture precursor. Examples of the solvent include water, alcohols, acetone, ammonia, ethers and glacial acetic acid. If the compound used in the release controlling agent is in a liquid or molten state, it is not necessary to use a solvent in the release controlling agent.

Release control agents have a detrimental effect on the properties of the substrate (e.g., by decoloring the substrate or by changing the shape or strength of the substrate), or by applying additional coatings of the substrate (e.g. after applying the insect repellent composition). Do not interfere with the processing of the substrate).

The amount of repellent compound present in the mixture precursor prior to application on the substrate to form the repellent composition is from about 0.05 to about 40 wt%, preferably from about 0.05 wt% to about 20 wt%, most preferably about 0.05 wt% To about 10% by weight (wet weight). The amount of the insect repellent compound present in the insect repellent composition after application to the substrate and optionally drying is from about 0.1% to about 80% by weight, preferably from about 0.1% to about 40% by weight, most preferably from about 0.1 to about 20% by weight. It is in the range of% (dry weight). All percentages are by weight.

Examples of substrates to which the mixture precursor can be attached include paper, cardboard, cardboard boxes, and their respective components, such as liners or media, plastics, plastic sheets, fabrics, metals such as aluminum, additional layers on the surface or Materials such as metallized films which may have a coating. The substrate is preferably present in the form of a container holding food for adults, children and animals. Examples of containers include foldable cardboard boxes, cardboard boxes, grooved cardboard boxes and boxes, sacks, bags, fiber moldings, compression trays, flexible packaging boxes, plastic and aluminum packaging boxes and containers. The substrate may also be present in the form of an object that can be placed in the area to be insect repellent, for example, a sample of paper, cardboard, plastic or metal placed in a food reservoir, shelf or building.

Examples of methods for coating controlled release insect repellents with mixture precursors include spray nozzles, rod coaters, blade coaters, air knife coaters, roll coaters, multi-roll transfers, controlled and unloaded loads, and wet bath immersion. , Curtain coaters, and vacuum and non-vacuum impregnation methods. If the emission control insect repellent device is a packing box, printing may be performed on the packing box. Printing methods that can be used in the present invention include gravure, flexography, screens, typography, web offsets, sheet fed offsets and ink jets.

The release rate of the active ingredient vapor from the insect repellent composition may also be controlled by attaching a directional barrier to the release controlled insect repellent device. Such barriers may also control the direction in which vapor is released. The barrier film material may be part of the substrate or directly attached to the top of the controlled release insect repellent device. The barrier material may be made of foil in the case of a complete barrier, or may be made of films, paper, coated substrates, or even solvent, solvent-free or aqueous applied liquid coatings, including multilayer films, if they are less than a complete barrier. Can be. Further examples of barrier films include aluminum foil, paper, polymer films or layered structures thereof. Examples of polymer films include polyethylene, polyester, polypropylene, polyvinyl alcohol, ethylvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate and layered structures thereof. Special barrier films tested are aluminum foil, polyethylene, polyester film, polypropylene film and paper. The paper tested was coated with an aqueous and non-aqueous solvent barrier coating.

Examples of insects to which the composition of the present invention can be applied include insects such as mites (for example, European dust mites, Dermatophagoides pteronyssinus, American house dust mites, and dermatopagoides parina) Dermatophagoides farinae) and fungal mites, Tyrophagus purescentiae, moths and moth larvae (e.g. gallery moths, Plodia interpunctella) (species = lepidoptera: Pyralidae (lepidoptera: pyralidae)}, weevil (e.g. rice weevil, Sitophilus oryzae), beetle (e.g. soybean beetle, Callosobruchu kinensis (Callosobruchus) chinensis) and garlic beetles, Stegobium paniceum) and house fly (Musca domestica).

The controlled release insect repellent device of the present invention is used to repel insects from food, tobacco or other consumables. The controlled release insect repellent device of the present invention may be in direct contact with food or other consumables (eg boxes for baby grain foods) or may be adjacent to food (indirect contact, eg on shelves). .

Example 1

An experiment was conducted to test the efficacy of methyl salicylate as a repellent against H. pyramid moths in controlled release insect repellent devices of the present invention. The purpose of this study was to evaluate pure (reagent grade) methyl salicylate as insect repellent, pH stabilized (reagent grade) methyl salicylate as insect repellent, and two ratios (0.1 v / v and 0.2 v as insect repellent). / v) methyl salicylate and uncured (undried) release controlling agent 45% solids (high solids, "H / S") and 10% solids (low solids, "L / S") To evaluate two mixtures of

Method and material

The study of efficacy was performed in a plastic petri dish test site (radius = 10 cm, height = 2.54 cm) with a plastic lid (FIG. 1). The lid was divided into four quadrants equipped with through vents and with felt markers. The quadrants were numbered 1-4 and treatment doses were always placed in the outer center of number 1.

Whatman 1 filter paper, which fits the inside diameter of the test site, was used as the lower substrate. Whatman 1 filter paper of 2.54 cm x 0.5 cm x 0.05 cm was folded in a z shape and placed in the center of quadrant 1 to be used as a treatment platform. The platform lifted the dose about 1.5 cm apart from the substrate to facilitate evaporation without direct lateral contact with the insect.

At the beginning of each experiment, one of 0.5 treatment doses of 0.5 mL each (3-5 repetitions) was aliquoted onto the platform with a pipette as follows: 0.1 methyl salicylate in ethyl alcohol (70%) (Reagent grade) (positive control), 70% ethyl alcohol (solvent control), pH stabilized 0.1 and 0.2 methyl salicylate (= 4 treatment groups) or H / S in H / S and L / S polymer mixtures: L / S (v / v) mixture (polymer control).

Twenty Gallop moth adults were aspirated from the breeding vessel, anesthetized with CO ₂ and carefully placed in the chamber before placing the treatment dose into the test site. The insects were acclimated at about 25.6 ° C. (78 ° F.) for at least 5 minutes.

The treated material was aliquoted onto the platform with a pipette and then the number of galaxies moths in the treated quadrants for each of the other three test quarter quadrants was measured at time intervals of 1 minute, 5 minutes, 10 minutes and 15 minutes. If the treatment dose was insect repellent, on average more moths were found in quadrants 2, 3 and 4.

All data were plotted and then listed in standard statistical summaries prior to performing variance analysis with a pair of T tests and / or mean separations.

The "ineffective" response was found, on average, to have the same number of gallery moths in each quadrant. If there is an insect repellent effect, it has been found that in one quadrant where the treatment dose is present, there are significantly fewer moths than other quadrants.

Typical examples for all cases containing methyl salicylate are shown in FIG. 1 and presented in Table 1 below.

TABLE 1

Table 1 shows that after 1 minute, the average number of moths found in the treated quadrant was 2 compared to the number 5 in quadrants 2, 3, and 4. The control moth distribution among the four quadrants averaged 4.7 ± 0.62 and it is noted that there was no difference between the control quadrants but a significant difference (p≤0.05) from the treated quadrants. This shows a powerful insect repellent effect.

After 5 minutes, on average, there are two adult moths in the treated quadrant, while five in the other quadrants, thus maintaining a strong insect repellent effect.

Moth adults were adapted, anesthetized or lethal from 10 minutes to the end of the test at 15 minutes. Certainly the dose was too high to prevent receptor attenuation and / or death caused by it.

Tables 1 and 3 reflect typical mean lethality in all cases containing methyl salicylate in ethyl alcohol or release control agents. This treatment left the moths dead within 10 minutes and gradually increased with exposure time. After 15 minutes, the average mortality rate was 35%.

Discussion and conclusion

Methyl salicylate is a powerful insect repellent of gallic moth adults. This is fully clear in all experiments and in each iteration of these experiments. At high doses (0.2v / v), methyl salicylates resulted in hyperactivity, impingement, avoidance behavior and ultimate lethality. At half the rate (0.1 v / v) treatment mixture, this symptom was delayed in time and intensity, but occurred in all treatment replicates.

Both reagent grade methyl salicylate and pH stabilized methyl salicylate formulations cause greater mortality than the polymer formulations. The two-day formulation also adapts moths in a shorter time than other formulations. This means that the polymer slows the release of methyl salicylate into the atmosphere. Therefore, the polymer extends the insect life of methyl salicylate.

No restraint and lethal phenomena were observed in the control group. In other words, ethyl alcohol as the solvent for reagent grade methyl salicylate or a mixture of H / S and L / S release controlling agents alone does not cause death. However, mixtures of all proportions of methyl salicylate with release controlling agents resulted in death.

Example 2

Experiments were conducted to determine the effect of the insect repellent composition of the present invention on the invasion of granulated moths into packaged infant cereals (banana rice). Moths are attached to food packages and lay eggs on them. The eggs hatch to lay larvae in the package, leaving holes, leaving the food exposed to the environment. After the food is eaten, the larvae grow, are usually silked by stripping 4-5 times, and then pupate into adult moths. The moth larvae grow into chrysalis in the food packaging and then become adult moths measuring 1.25 cm (½ inch).

Ecological Cycle of Gallery Moth

Preparation of Insect Repellent Composition

Insect repellent composition precursors were prepared by mixing the release control agent with the repellent compound. In some compositions, other additives may also be used.

Composition A was prepared by mixing additives and release controlling agents in the following fractions: 80% by weight of styrene acrylic resin (release control agent), 10% by weight of nonionic poly wax (coupling agent) and 2% aqueous solution of sodium alginate 10% by weight (thickener). The sodium alginate solution took 20 seconds, a viscosity of # 3 Zahn cup (i.e. 20 seconds for 44 mL of solution to pass through the opening at the bottom of a metal cup 0.38 cm (0.148 inch) in diameter; Measured using). Thereafter, the release controlling agent mixture was added to the insect repellent compound (methyl salicylate) and the solvent (deionized water) to form Composition A.

Composition B was prepared by mixing the release controlling agent directly with the insect repellent compound. Release control agents are commercially available primers and the repellent compound is methyl salicylate.

Compositions A and B were prepared using three different concentrations of insect repellent compounds. All of these compositions contain a 90% release controlling agent mixture and one of the insect repellent compounds (wet weight) of 0.5%, 2.5% or 5.0% with the remaining amount of solvent. The viscosity of the composition before solvent addition is 18-20 seconds, the viscosity of the # 2 Zahn cup (i.e. 18-20 seconds through which 44 mL of solution passes through the opening at the bottom of the metal cup 0.27 cm (0.108 inch) in diameter). Hangs). The pH of the final composition is about 9 to about 9.5.

Processing of carton

The insect repellent compositions precursors A and B were applied to the cardboard by two methods A and B respectively, 1% of three different dry weight concentrations (0.976 kg coating / m ² cardboard surface (0.2 lb / 100 ft ² ), 5 % And 10% dry weight] were prepared on the substrate having a pesticide composition. As shown in FIGS. 4 and 5, the substrate consists of a cardboard 1 coated with a polyethylene inner coating 2 and an outer clay coating 3. The insect repellent composition 4 was applied to two parts of the substrate. 4 shows the results of method A, in which the polyethylene coating 2 was extruded onto the inner side of the cardboard and at the same time the insect repellent composition 4 was applied onto the outer clay composition 3 of the cardboard box. 5 shows the results of Method B, in which the insect repellent composition 4 was applied to the back of the cardboard before the polyethylene 2 was extruded on the back of the cardboard (ie, the polyethylene was extruded onto the repellent composition). The cardboard was then converted to cardboard boxes of the type commercially available for cereals, which had a polyethylene coating covering the back of the cardboard and a clay coating on the outside of the cereal box.

Insect repellent-treated cardboard was filled with banana rice baby cereal food and sealed with glue.

Gallery Moth Penetration Test

After six weeks or more after the cardboard was treated with the insect repellent composition, the cardboard was exposed to the gallery moth in the test chamber. Treated cardboard boxes were divided into eight groups (two controls (non-treated group), three groups treated with the insect repellent composition by Method A and three groups treated by Method B). One group of controls was separated separately in a separate chamber and the other group was left standing with the treatment group for testing.

The difference between each of the three groups treated by both methods A and B is the methyl silicate content in the dried coating of 1%, 5% and 10%.

The total duration of the invasion test was 8 weeks. From the start of the test and at the beginning of each subsequent week, new adult moths were placed in the test chamber. At the beginning of the test, these moths can produce larvae (moth invasion stage) at a measurement rate of 156 / box.

In cardboard boxes randomly placed in the test chamber, six cardboard boxes for each group were taken out and sampled at 0,1,2,4,6 and 8 weeks. The total number of cartons used was 288 cartons, of which 48 cartons were not exposed to the insect repellent composition and the number of larvae was about 37,500.

When each new moth was added, the total number of cartons in the test chamber decreased due to sampling, but the total number of larvae did not change. Thus, in the last week of the test, the ratio of larvae to cardboard boxes that increased constantly with each sampling increased from 156 to 1,250. In addition, the remaining cartons until the completion of the 8 week test were exposed to a total of 5,600 larvae / cartons for the duration of the test.

The spacing between the cartons was about 1.3 cm (0.5 inches) during the first week of the test and gradually increased with each sampling due to the removal of the sampling carton, reaching about 15.2 cm (6.0 inches) at the end of the test. The conditions in the test chamber were controlled similarly to those in the home shelf: the temperature was approximately 25 ± 1.9 ° C. (77 ± 3.5 ° F.) and the air was changed completely 12 times daily.

Invasion of cardboard boxes by moth larvae is the percentage of cartons invaded by moths at any stage of the development phase of moths, the total number of larvae per carton, 0,1,2,4,6 and At 8 weeks, the growth and development of the larvae was described as normal. The cartons were incubated for an additional 2 weeks in each sealed plastic bag to grow the larvae large enough to count the larvae. The results are shown in Tables 2a and 2b below.

TABLE 2a

TABLE 2b

The results presented in Table 2 show that the cartons were not invaded at all during packaging and transportation, as evidenced by the absence of invasion at the beginning of the test that occurred approximately two months after treatment with the insect repellent composition.

Separately isolated control cartons were invaded by 33% after the first week by 2-3 normally developed moth larvae per carton. After two weeks, the percentage doubled to 67%, and after six weeks it was invaded by more than 15 moths normally developed per carton.

A non-isolated control carton tested by placing in the vicinity of the treated carton was 17% invasive except that no larvae were present after 2 weeks by only one moth larva that was stunted after 1 and 4 weeks. Indicated. After 6 weeks the cartons showed 17% invasion by one moth larva that develops normally. After 8 weeks, 83% of the cartons were invaded by one moth that developed normally per carton. Slower intrusion of the control carton placed near the treated carton means that the treated carton imparts any second protection to the control carton.

Treated cardboard boxes invaded only one larva that was stunted after 2 and 6 weeks, but did not invade normally developing butterfly larvae until 8 weeks later. In addition, cardboard boxes treated with the insect repellent composition containing the maximum concentration of the insect repellent compound (10%) contained only moths that were stunted after 8 weeks when treated using Method B and never treated using Method A. Did not contain moths.

The performance of the insect repellent composition in preventing the penetration of cardboard boxes is impressive given the various factors. The cumulative strength of the larvae (5,6000 per carton; from 156 per carton at the beginning of the test up to 1,250 per carton after 8 weeks of testing) is much greater than that of packaged food cartons. In addition, more than four months had elapsed until the application of the insect repellent composition to the cardboard box to complete the experiment. Eventually, the moths observed that when they were first introduced into the test chamber, they tried to run away rather than find food cartons. Therefore, if the carton is tested immediately after application by the insect repellent composition, the cumulative strength of the larvae is in the normal range, and if the larvae do not stay in the vicinity of the carton, the invasion of the treated carton is significantly reduced. .

According to the present invention, there is provided a controlled release insect repellent device that is effective for insect repelling, is comfortable for most people upon contact, and does not have a harmful effect on the environment.

1 shows the design of a test site used to test the efficacy of methyl salicylate as a repellent against Indianmeal moth.

FIG. 2 shows the reaction of Hwarangmok moth to methyl salicylate.

FIG. 3 shows the exposure effect of Gallery Moth to the controlled release insect repellent device of the present invention containing methyl salicylate.

4 shows a first embodiment of the controlled release insect repellent device of the present invention.

Figure 5 shows a second embodiment of the controlled release insect repellent device of the present invention.

<Explanation of symbols for the main parts of the drawings>

1: carton

2: internal coating

3: exterior clay coating

4: insect repellent composition

Claims (1)

One or more essential oils for insect repelling, and 0.1 to 80% by weight (dry weight) of the active ingredients of the essential oils, and A release controlling agent for controlling the release of the essential oil to a predetermined low level to prolong the useful period for insect repelling Controlled release insect repellent composition comprising a.

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