A method of producing and using a solution, and the solution itself, for extending the shelf life of fresh flowers, fruits and vegetables after they are harvested which includes the steps of extracting juice from the flowers, flowering plant parts, fruits or vegetables, filtering the juice, disintegrating the parts from which the juice is extracted, extracting an enzyme or enzymes from the parts using a solvent without the denaturing the enzymes, removing the parts and mixing the remaining ingredients with the extracted juice.

1. Field of the Invention
The field of the invention is fresh cut flowers, fresh fruits and vegetables, and methods and compositions for maintaining their freshness and shelf life without refrigeration.
2. Description of Related Art
Since the beginning of mankind, agriculture has always played a major role in the everyday life of man particularly to fresh fruits and vegetables that are easily harvested. Modern agriculture has increased productivity in agriculture but has never reduced the huge losses in the post-harvest of fresh fruits and vegetables. These post-harvest losses are not new; they have always been a problem for mankind. In these days of rapidly enlarging populations in the poorest countries whose food supply is already short, the problem of post-harvest loses of fresh fruits and vegetables has become increasingly critical. Currently these post-harvest loses amount to thirty-five percent (35%) in industrialized countries to seventy percent (70%) in under developed countries.
In the early days of horticulture in today s industrialized countries, heavy losses occurred in much the same manner as they do today in developing countries. Increasing industrialization in technologically-advanced nations gradually brought improvements in crop handling. Elaborate harvesting equipment replaced the crude harvesting tools. Collection centers were strategically established in major producing areas. Containers were remodeled to add more protection to the fresh fruits and vegetables. Commercial storage plants were installed and grade standards adopted. Engineers and economists became more and more aware of raw material behavior. Advances in refrigeration technology in the developed countries made possible the establishment of cold chains for the entire post-harvest and handling operations. At the institutional level, post-harvest research was initiated. Pilot packing houses were installed, coupled with the development on intensive training programs. The improvement of product quality and reduction in post-harvest losses became the main concern of producers, middleman, marketing specialists and consumers. Today, enormous volumes of quality horticultural fruit and vegetable crops produced in technologically advanced countries are made available to millions of people through improved post-harvest handling. Thus, historically and by necessity, post-harvest technology is part of the normal development processes in agriculture.
These handling processes are not fully recognized in less-developed countries. In such countries, agriculture may be characterized as disjointed. Production is not linked with marketing. With highly perishable crops like fruits and vegetables, storage, packing, transport, and handling technologies are practically non-existent. Hence, considerable amounts of fresh fruits and vegetables are lost after harvest. Post-harvest, loss-prevention technology measures have become more important than ever.
It is distressing to note that so much time is being devoted to the culture of plants, so much money spent on irrigation, fertilization, and crop protection measures, only to be wasted about a week after harvest. It is, therefore, important that post-harvest technology and processes be given much more attention than current production practices.
Fresh fruits and vegetables have many similarities with respect to their compositions, methods of cultivation and harvesting, storage properties, and processing. In fact, many vegetables may be considered fruit in the true botanical sense. Botanically, fruits are those portions of the plant which house seeds. Therefore, such items as tomatoes, cucumbers, eggplants, peppers and others would be classified as fruits on this basis. However, the important distinction between fruit and vegetables has come rather to be made on usage basis. Those plant items that are generally eaten with the main course of a meal are considered to be xe2x80x9cvegetablesxe2x80x9d. Those that are commonly eaten as dessert are considered xe2x80x9cfruitsxe2x80x9d. This artificial distinction is made by the food processor, certain marketing laws, and the consuming public. Fruit contains natural acids, such as citric acid in oranges and lemons, malic acid of apples, and tartaric acid of grapes. These acids give the fruits tartness and slow down bacterial spoilage. Organic acids also influence the color of fruits since many plant pigments are natural pH indicators. Carbohydrates are the main component of fruits and vegetables and represent 90% of their dry matter. Water is also present in fruits (between 80 to 90%) and in vegetables (generally, between 90 to 96%). More mineral substances are present in vegetables than in fruits; but enzymes that are present in all fresh fruits and vegetables are the biological catalyst that promote most of the biochemical reactions which occur in fresh fruits and vegetables.
Some properties of enzymes in fresh fruits and vegetables are the following.
1. In living fresh fruits and vegetables, enzymes control the reactions associated with ripening.
2. After harvest (unless destroyed by heat, chemicals, or some other means), enzymes continue the ripening process. In many cases, fruit ripens to the point of spoilage, such as soft melons or overripe bananas.
3. Because enzymes enter into a vast number of biochemical reactions in fresh fruits and vegetables, enzymes may be responsible for changes in flavor, color, texture, and nutritional properties.
4. The heating processes in fresh fruits and vegetables manufacturing and processing are designed not only to destroy micro-organisms, but also to deactivate enzymes and so improve the fruits and vegetables storage stability.
Once the fruit or vegetable has left the tree, the organoleptic properties, nutritional value, safety, and aesthetic appeal of the fruit deteriorates in varying degrees. The major causes of deterioration include the following:
(a) growth and activity of micro-organisms;
(b) activities of the natural food enzymes;
(c) insects, parasites, and rodents;
(d) temperature, both heat and cold;
(e) moisture and dryness;
(f) air and in particular oxygen;
(g) light; and
(h) time.
The rate at which foods spoil, if proper measures are not taken, is indicated in table 1.0 below. The table shows the time in days of the generalized storage life at seventy degrees Fahrenheit (70xc2x0 F.) with a normal humidity of 60%.
Flowers are a colored, sometimes scented, part of a plant that contains its reproductive organs. It consists of a leafy shoot with modified leaves, petals, and sepals surrounding male or female organs, stamens, and pistils. There are about 200,000 species of flowers, classified in many different families. However, only about 1,000 flowers are used commercially worldwide due to the short shelf life associated with them. The most common uses are horticultural, ornamental and as gifts (such as roses), gastronomical reasons (such as lettuce and artichoke), or as vegetable oil (like sunflower oil). Flowers are grouped into an inflorescence (flower cluster) called the head, or capitulum, which resembles, and functions as, a single flower. The flowers within the head are called florets. There are two types of florets. The first, called a disc floret, has a tubular corolla (set of petals) with equal lobes. The second type, called a ligulate or ray floret, has one side of the corolla tube extended at the apex to form a long, petal-like strap. The calyx (floral envelope) that surrounds the individual floret in a head is usually reduced to a ring of scales or bristles called the pappus, which often aids the distribution of seeds. In the common dandelion and thistles the pappus consists of fine bristles that enable the fruit to float through the air. In other species it is barbed, causing the fruit to stick to passers-by. The anthers (pollen-producing parts) are joined to form a tube through which the style (part of the female flower part) extends. The anthers release the pollen into the tube, and as the style elongates it pushes the pollen upward out of the tube, making it available to insect pollinators or to wind dispersal. The stigmas (pollen-receiving areas) of the style are located on two branches of the style tip, and these branches separate after elongation. Thus, self-pollination is usually avoided, although in some instances pollen travels backwards into the pollen-bearing anther tube to allow this to occur. The pistil (female flower part), which has a single ovary, bears the other flower parts on its apex. After fertilization it matures into a hard-coated fruit that bears a single seed. Plants like humans also have need for water. If flowers do not receive water, they will and ultimately due. For some plants, such as tomatoes, a quick watering revives them within a few minutes to an hour, whereas more sensitive plants may never recover. Unlike animals, plants do not have a rigid skeleton. Woody plants, such as trees and shrubs, have hardened cell walls with secondary growth to give them rigidity. Herbaceous plants, on the other hand, have very flexible cell walls which are rigid only when the plant""s cells are filled with water. Animal cells under the same amount of internal pressure would burst, but plant cell walls are much stronger and easily withstand this pressure, which is called turgor pressure. In order to maintain turgor pressure plant cells need an ample supply of water. Plants continuously lose some of their water through a process called transpiration. Like all organisms, plants must breathe. Air is exchanged through small openings called stomata (stoma, singular), located on the undersides of leaves. Stomata can be opened or closed by a special pair of cells called guard cells. Unfortunately, not only does air pass in and out, but also water. On a hot day especially large amounts of water can be lost. If the plant is unable to replenish the water being lost the guard cells begin losing their turgor pressure. Soon thereafter, if water is still unavailable the plant wilts as many other cells begin losing their turgor pressure. There are many adaptations used by plants to prevent water loss than in addition to the simple approach of closing the stomata. One of the more familiar approaches is to store large amounts of water either in the stem, as in cactus or cacti, or in the leaves and stem, as in stonecrops (sedum) and other succulents. A natural waxy leaf covering is effective in preventing water loss in some plants. The common sagebrush, as well as a number of other desert and chaparral plants, often have dense, light colored hairs covering the leaves. This prevents not only water loss, but deflects some of the sun""s heat, which can also prevent evaporation. Even more intricate mechanisms are used by some plants. The stonecrops and other members of the Crassulacea,e among a number of plants in other families, use a special type of photosynthesis called Crassulacian Acid Metabolism or CAM. This alternate photosynthetic mechanism allows the plant to open their stomata at night, while keeping them closed throughout the day, when water loss would be at worst. Still other plants simply avoid the whole water problem by either growing only when water is abundant (so-called ephemerals) or by becoming entirely aquatic as in pondweeds (Potamogetonaceae) or pond lilies (Nymphaeaceae). In fact, aquatic species occur in most flowering plant families. An specially big challenge for most plants is obtaining water from salty soil or saltwater. Very few plants can tolerate very much salt in their surroundings. First, molecules of any substance have a tendency to migrate from areas of high concentration to areas of low concentration. This phenomenon is called diffusion and is best observed by dropping a small amount of red food coloring into a glass of water. After a few hours, even without agitating the water at all, the food coloring diffuses evenly throughout the water. Water also diffuses from areas where there there is more water to areas where is less water. In water this process is referred to as osmosis. In saltwater there is less water per given volume then there is in pure water. If some pure water is separated from some saltwater by a membrane that allows just water to pass and not salt, and interesting phenomenon occurs. Water gradually flows from the pure waterside into the saltwater side. In fact, it will continue to flow, but when a moderate amount of pressure is applied the flow will stop, the amount of pressure required being a measure called osmotic pressure. We can apply this concept to what happens to a plant in wet soil. If the water in the soil is fairly pure, with only a small amount of salt and other dissolved material, water will tend to flow from the soil into the roots of the plant. This is because the water already in the plant root has a lot more solid matter dissolved in it and the water flows from the fairly pure soil water to the soupy water already in the root by osmosis. In salty soil the situation is reversed. The soil water now has more dissolved in it than the water in the root and osmosis is reversed. Water flows out of the root into the soil. As a result the plant wilts and eventually dies from lack of water, even though there may be large amounts of water around. Some plants have adaptations which allow them to survive in the presence of large amounts of salt. Surf grass and eel grass (both Zosteraceae) are two flowering plants that actually live submerged in saltwater, keeping the salt concentrations in their leaves and roots fairly similar to the surrounding seawater. Mangroves comprise a large number of species whose roots are bathed in saltwater as well. Others, like pickleweed, can tolerate even higher levels of salt found in the twice-daily exposed soils of the salt marsh. They accomplish this feat by keeping salt concentrations within their stem and roots even higher than the surrounding water in the salt marsh soils. Saltgrass, a little less tolerant, survives the high salt concentrations in soils above the high tide line by excreting salt on the surfaces of their leaves. Other plants, less salt tolerant, are still capable of surviving in soils that are deadly to most plants. Plant breeders are very interested in how halophytes deal with salty soil. It is hoped that some of the genes responsible for salt tolerance will be located so that they can be put into important crop plants. If important crop plants could be developed to have salt tolerance, many currently unusable land could be farmed. Irrigated land gradually builds up salt and eventually becomes unusable, and such genetically engineered plants could prolong the life of irrigated land. Most cactus do come from warm weather low rainfall areas of the world although there are exceptions. There are no known fossils of cactus, and it is not known with certainty when they developed the unique adaptations that enable them to live in the harsh environments that many of them survive in. Many scientists believe that the cactus developed their physiological traits in response to changing climatic conditions several million years ago. The major traits that people see when they first observe cactus is the abundance of spines in many species. These spines serve several uses. They guard against most browsing herbiverous animals by making the plant difficult and dangerous to chew. The spines also help to shade the plant, helping keep internal heat down. Finally the spines also can channel the infrequent rains to the base of the plant. Another easily identified characteristic of many cactus is a waxy coating that surrounds the plant over the skin, which often has a bluish cast to it, and may be damaged by careless handling. This is called a glaucus bloom and helps to reduce evaporation by the plant. This holds in more of the precious moisture so rare in the desert. All advanced plants have leaf holes called stomata. These holes are what open to permit entry and exit of various gases and moistures. Un cactus these stomata close tighter than in most plants further reducing the loss of moisture in the heat of the day. Another thing that cactus can do is to store up lots of water when it does fall. Many have the ability to open themselves up accordion style to hold massive amounts of water. Then when the plant is losing water, the pleats of the accordion fold up shading the plant more and reducing surface area exposed to the sun. When the plant is stressed and not getting enough water it will often bend over as the hygroscopic (water filled) pressure inside the plant diminishes. The hygroscopic pressure is what holds the plant up erect. As it lessens the plant loses its rigidity and can no longer stand erect. As it bends over its exposure to the sun is reduced, much of it is shaded by the overhead portion such that moisture loss is further lessened. Root behavior is another adaptation that cactus have made in order to live. They tend to have roots that spread laterally for quite a ways and may exist in a suspended state until the rains activate them, a small amount of moisture will cause the feeding roots to quickly grow out from the main roots. These feeders bring in the water and its dissolved minerals and nutrients. After the rain is gone and as the soil dries these feeder roots die and disappear enabling the plant to live on its stored water without having to spend energy and moisture keeping these roots alive that may not be needed for many, many months. The above mentioned main characteristics of flowers are relevant to the reader to understand the purpose of this invention and the principles taught in my U.S. Pat. No. 6,123,968. The instant invention is to a process to create a composition, and the resulting composition for extending the shelf life of fresh cut flowers and fresh fruits and vegetables without the use of refrigeration. Fresh cut flowers, like fresh fruits and vegetables are also lost in enormous quantities worldwide once they are severed from the mother plant, i.e. harvested. Thus, there is clearly a worldwide need for the present invention in that it is going to dramatically reduce, and in some cases eliminate the need for refrigeration between harvest and consumption.
As soon as produce is harvested, the processes leading to breakdown begin, and cannot then be stopped; the rate at which breakdown occurs can, however, be slowed to minimize losses. The most common commercial methods to slow down the enzymatic processes follow:
1. Refrigeration at all points of receiving, distributing, and retailing the fresh fruit, flowering plants and vegetables. Although, this is a very expensive method, it is the most common. Only 15 to 20% of all harvested fruits, flowering plants and vegetables use refrigeration.
2. Care to prevent cutting or bruising of the fruit, flowers and/or vegetables during picking or handling.
3. Packaging or storage to control respiration rate and ripening of fruits, flowers and vegetables.
4. Use of preservatives to kill micro-organisms on the fruits, flowering plants and vegetables. In other words, fungicides are applied as food waxes and other applied substances to supposedly improve the appeal of the fruits, flowers and vegetables with consumers.
Fruits can be classified as climacteric and non-climacteric. Climacteric and non-climacteric refers to two distinct patterns of ripening. In non-climacteric fruits the process of maturation and ripening is a continuous but gradual process. In contrast, climacteric fruits undergo a rapid ripening phase when triggered by enzymatic changes. The onset of climacteric ripening is thus a well-defined event marked by rapid increase in the rate of respiration and the natural evolution of ethylene gas by the fruit at a point in its development known as the respiratory climacteric. The importance of the respiratory climacteric is that fruits such as bananas may be held at a reasonable temperature when in the green state, but, as they begin to ripen, they will rapidly increase their respiration and generate much more heat. The consequence may be that this heating cannot be controlled and even more respiration will occur in a chain reaction, rapidly leading to spoilage of the fruit in a very short time. Once climacteric fruits start to ripen, very little can be done except to market them for immediate consumption. Ethylene is present in all fruit and is recognized as the central fruit ripening hormone which, in climacteric fruits, can actually initiate ripening when present at concentrations as low as one-tenth to ten parts per million (0.1-10 ppm).
Non-climacteric fruits also respond to ethylene application by increasing their respiration rate. However, the actual ripening process is triggered by the fruit itself. As well as being involved in ripening and increasing the respiration in fruits, ethylene also plays an important role in all plant materials and is produced in response to stress from wounds and injuries. In other words, ethylene produced by wounding or stressing may also trigger ripening in the damaged fruit as well as the undamaged fruits around it. Damage one green fruit in a box and the whole box load may ripen prematurely.
For this reason, good ventilation of fresh fruits with fresh air, refrigerated if necessary, is vital to ensure that ethylene levels do not build up to significant levels during storage and transport. Ethylene can also adversely affect certain vegetables. Carrots for example develop bitter flavors. Parsley and other leafy herbs will rapidly wilt when exposed to ethylene in stores and during retail display. Table 1.1 gives listings of common climacteric and non-climacteric fruit and vegetable fruits.
For all of the above-mentioned reasons and facts, the huge losses of fresh fruits and vegetables are a worldwide problem that needs to be solved with an inexpensive and simple method of application. Thus, there is clearly the worldwide need for the present application in that it is going to create an impact as large as the introduction of refrigeration to the worldwide, fresh fruit and vegetable industry.
The invention applies a process that naturally the enzymatic processes of ripening that occur in all fresh flowers, fruits and vegetables. The invention encompasses methods of making solutions, the solutions themselves, and the methods of using the solutions.
The invention also applies a process that naturally extends the shelf life without much water usage and without much moisture and also without the use of refrigeration for fresh cut flowers and fresh fruits and vegetables once they have been removed from the mother plant.
The naturally-occurring process being harnessed is the retarding of ripening in flowers/flowering plants, fruits and vegetables. Enzymes are protein catalysts that regulate chemical reactions in flowers/flowering plants, fruits and vegetables. Fruits and vegetables contain enzymes that advance ripening. Flowers/flowerings plants, fruits and vegetables also contain enzymes that retard ripening. The enzymes that advance and the enzymes that retard tend to offset each other. In most flowers/flowering plants, fruits and vegetables, both types of enzymes are present. An object of the invention is to harness and/or re-create the effect of the enzymes that retard ripening. Another object of the invention is to reduce or eliminate the effects of the enzymes that advance ripening.
In certain flowers/flowering plants, fruits and vegetables, the ratio of positive enzymes versus negative enzymes is greater than one. The flowers/flowering plants, fruits and vegetables with greater ratios are better suited for raw materials used to prepare the solution. Examples of fruits having greater ratios are limes, garlic, and onions. The following fruits and vegetables have been found to have produced efficacious solutions: limes, oranges, grapefruits, lemons, tangerines, pineapples, onions, and garlic. Cactus solutions made from combinations of the above-listed fruits and vegetables also work. The best time to process the fruits and vegetables to make a solution is when the fruits and vegetables have just ripened.
Also, some of the natural ingredients of the solution made out of fresh lime peels are very effective in controlling or killing surface bacteria, mold, and yeast which also can shorten the lifetime of the fruit.
Also, the naturally-found ingredient, d-limonene, is an excellent insect repellent. D-limonene is in relatively-high concentrations in limes. This also will increase the lifetime of the fresh fruit due to a lessening of the susceptibility of the skin to attack. Flying insects rarely attack a lime tree or the limes within the lime tree because they contain d-limonene.
The fruit enzymes are responsible for the many changes to the color, the odor, the taste, and the ripening of the fresh fruits. Once these enzymes become neutralized by other enzymes, the shelf life of the fresh fruits and vegetables can be extended from three to eight weeks depending on the fruit. The metabolism of the fruit will slow down by about 90%, causing the ripening and decaying process to slow down.
A method of producing the solution involves the following steps. First, the juice is extracted from the a part or parts of the plant, fruit or vegetable. Next, the juice is filtered. Next, any remaining parts are disintegrated. Next, the enzymes in the disintegrated parts are extracted with a solvent. The solvent should be chosen by its ability to dissolve as much of the enzymes as possible, while not dissolving the other flower, fruit or vegetable components. The solvent should not denature the enzyme. A ten-percent (10%) aqueous ethylalcohol solution is an example of a suitable solvent. Next, the disintegrated parts should be stirred in the solution allowing for full absorption of the enzymes into the solvent. Next, the solution and any disintegrated parts should be separated by a suitable method such as filtering. Next, the juices separated earlier can be added to the solution. The amount of dilution is governed by factors such as the method of application and the type of flower, fruit or vegetable being protected. Next, color agent(s) can be added to the solution to improve the solution aesthetically. Next, a wax or other application can be dissolved into the solution. The wax agent helps the application of the solution to the flower, fruit or vegetable and its adhesion to the flower, fruit or vegetable. Next, the solution can be quality controlled. In quality control, the amount of enzymes can be verified as well as any other ingredients. In addition, during quality control, the amount of contaminants can be verified. Finally, the solution is packaged for use or distribution. Because the solution utilizes plant enzymes that denature at around one hundred-thirty degrees Fahrenheit (130xc2x0 F.), the process of making the solution is always done near room temperatures. The results retain ninety to ninety-five percent (90-95%) of the enzymes that are found in the natural state of the extracted flower, fruit or vegetable.
In accordance with these and other objects which will become apparent hereinafter, the instant invention will now be described with particular reference to the accompanying drawings.

Composition for preserving fresh cut flowers, fresh fruits and vegetables without the use of refrigeration


There are described a flowable composition for controlling harmful insects and representatives of the order Acarina, comprising at least one pesticidally active compound, one or more signal substances selected from the group consisting of pheromones, kairomones and attractants, a UV absorber or a UV absorber mixture and, if appropriate, one or more additives selected from the group consisting of viscosity-regulating thickeners, fillers, solvents and other formulation auxiliaries,

The present invention relates to a novel pesticidal composition for controlling harmful insects and representatives of the order Acarina, and to a method of controlling these pests with the composition in question.
When controlling plant pests, in particular insects and spider mites in agricultural crops, especially in monocultures, it is an aim to keep the contact between not only the crop plants, but also their environment and the soil in which they grow, and the pesticidally active ingredients to a minimum. However, it is nevertheless intended to expose the pests themselves, which are mainly found on the plants, to the active ingredient as intensely as possible, for example by contact action or by action as a stomach poison. It is furthermore attempted to ensure that the adverse effects of the pesticidally active ingredients on beneficial animals and warm-blooded species are not substantial. To achieve these aims, pesticides and control methods have been proposed whose principal is that the behaviour of the target pests can be controlled or altered, with the aid of signal substances, for example using pheromones, in such a way that the pests are led to a source of a pesticidal active ingredient, which source is provided in separate areas within the cultivated area to be protected (so-called attract-and-kill methods, EP-A-376 888). Such methods have been successful in particular for controlling adult pests. However, the control of larvae of these pests, using these methods, is very poor indeed since these larvae are generally of low mobility and will therefore hardly find the source of the signal substances and thus the pesticide. Naturally, in contrast, eggs of those pests cannot be controlled at all using such methods. Thus, if one intends to achieve that, on the one hand, not only the crop plants to be protected, but also the soil in which they grow, come into as little contact as possible with pesticidally active ingredients but, on the other hand, the pests found on the plants are exposed to the active ingredients as intensely as possible while simultaneously leaving the beneficial animals unharmed, the method of choice will be the attract-and-kill methods described in the literature. However, as discussed, one will have to accept that it is hardly possible, using this method, to control the larvae present in the crop, and not at all possible to control the eggs which have been deposited in the period during which the crop has been treated with the composition in question. Thus, this means that the crop may be reinfested with the pest a short time after the treatment. There is therefore still a demand for a method of controlling pests which, in the manner described above, not only leaves plants and environment largely unharmed, but which is also capable of destroying not only the adults, but in particular the eggs and larvae, very especially preferably the eggs, of the pests so as to prevent the pest from spreading further.
The abovementioned shortcomings are overcome by control method and composition according to the invention. The invention relates to a flowable composition for controlling harmful insects and representatives of the order Acarina, comprising at least one pesticidally active compound, one or more signal substances selected from the group consisting of pheromones, kairomones and attractants, a UV absorber or a UV absorber mixture and, if appropriate, one or more additives selected from the group consisting of viscosity-regulating thickeners, fillers, solvents and other formulation auxiliaries,
which comprises 40 to 98% by weight of the UV absorber or of the UV absorber mixture,
0.01 to 30% by weight of one or more signal substance(s), and
0.1 to 20% by weight of one or more pesticidally active compound(s) selected from the group consisting of the compounds of the formula
in which
a is 0, 1 or 2 especially 0, where, if a is 2, the two radicals R1 are identical or different,
b is 0, 1 or 2, especially 0, where, if b is 2, the two radicals R2 are identical or different;
X is methylene, O, S or C(xe2x95x90O), especially O,
R1 is C1-C3alkyl, halo-C1-C3alkyl, C1-C3alkoxy, halo-C1-C3alkoxy, fluorine, chlorine or bromine, especially fluorine or chlorine;
R2 is halogen, nitro, C1-C6alkyl, phenyl-C1-C6alkyl, halo-C1-C4alkyl, C1-C3alkoxy, halo-C1-C3alkoxy, C2-C4alkenyl, C2-C4alkynyl, C1-C3alkoxyalkyl or C3-C6cycloalkyl, and
A is C1-C6alkyl, C2-C6alkenyl or C3-C6alkynyl, which are unsubstituted or substituted by a substituent selected from the group consisting of C1-C6alkoxy, C2-C6alkenyloxy, C3-C6alkynyloxy, xe2x80x94Oxe2x80x94Nxe2x95x90CH2, xe2x80x94Oxe2x80x94Nxe2x95x90CHxe2x80x94C1-C6alkyl, phenoxy, pyridyl, pyridyloxy, phenyl and phenyl, which is substituted by a substituent selected from the group consisting of C1-C6alkyl or xe2x80x94Oxe2x80x94CH2xe2x80x94Oxe2x80x94, especially pyridyloxy, C2-C6alkenyl or C3-C6alkynyl which are unsubstituted or substituted by a substituent selected from the group consisting of halogen, C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl and C1-C6aminocarbonyl;
A is a radical
where either
R3 is C1-C6alkyl, halo-C1-C3alkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C3alkoxy or C3-C6cycloalkyl, especially C1-C4alkyl, and R4 is hydrogen or C1-C3alkyl, especially hydrogen, or R3 and R4, together with the carbon atom to which R3 and R4 are bonded, are a ring having 4, 5 or 6 ring members, where the ring skeleton, which may contain a carbon-carbon double bond, is either constructed from carbon atoms only or may contain one oxygen atom and where the ring is unsubstituted or mono- or disubstituted by identical or different C1-C3alkyl; and
R5 is hydrogen or C1-C3alkyl, especially H; or
a radical
where R6 is C1-C6alkyl, phenyl-C1-C6alkyl, halo-C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C6alkoxy, phenoxy, phenyl-C1-C6alkoxy, halo-C1-C4alkoxy or C3-C6cycloalkyl, especially C1-C6alkyl or C1-C4alkoxy, in particular C1-C4alkoxy;
R7 is hydrogen, C1-C6alkyl, phenyl-C1-C6alkyl, halo-C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl,
C1-C3alkoxyalkyl or C3-C6cycloalkyl, especially H; and
Y is O or S, especially O;
in free form or in salt form;
isopropyl (E,E)-(R,S)-11-methoxy-3,7,11-trimethyl-dodeca-2,4-dienoate (methoprene); or
prop-2-ynyl (xc2x1) (E,E)-3,7,11-trimethyl-dodeca-2,4-dienoate (kinoprene);
of the formula
in which R20, R23 and R24 independently of one another are hydrogen, halogen, C1-C8alkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C8alkoxy, C1-C4alkoxy-C1-C4alkyl or halo-C1-C8-alkoxy, especially C1-C2alkyl; and
R21, and R22 independently of one another are H, C1-C8alkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl or halo-C1-C8-alkyl, especially H or C1-C4alkyl;
in free form or in salt form;
of the formula
in which
R10 is hydrogen or C1-C4alkyl;
R11, is hydrogen, C1-C6alkyl or C3-C6cycloalkyl
R12 is H, C1-C6alkyl or C3-C7cycloalkyl, or
R11 and R12 together are xe2x80x94CH2xe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94CH2xe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94Sxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94NHxe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94N(CH3)xe2x80x94CH2xe2x80x94 or xe2x80x94CH2xe2x80x94N(C2H5)xe2x80x94CH2xe2x80x94;
R13 is H or C1-C4alkyl, especially H;
X1 is N or C-E;
E is H or xe2x80x94CH(OH)-halo-C1-C6alkyl, especially H;
Y1 is CN or NO2, especially NO2; and
B is an unsubstituted or substituted aromatic or non-aromatic monocyclic or bicyclic heterocyclic radical which can contain, depending on the substitution possibility on the ring system, independently of one another one to three substituents selected from the group consisting of C1-C3alkyl, C1-C3alkoxy, halogen, C1-C3haloalkyl having 1 to 7 halogen atoms, cyclopropyl, halocyclopropyl having 1 to 3 halogen atoms, C2-C3alkenyl, C2-C3alkynyl, C2-C3haloalkenyl and C2-C3haloalkynyl having 1 to 4 halogen atoms, C1-C3haloalkoxy having 1 to 7 halogen atoms, C1-C3alkylthio, C1-C3haloalkylthio having 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio and cyano, especially halogen, very particularly chlorine; in free form or in salt form, if appropriate tautomers, in free form or in salt form;
of the formula
in which
c is 0 to 5, especially 3, where, if c is greater than 1, the radicals R14 are independent of one another, and
d is 0 to 5, especially 2, where, if d is greater than 1, the radicals R15 are independent of one another,
R14 is halogen, C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C6alkyl, C1-C8alkoxy, C3-C6cycloalkoxy, halo-C1-C8alkoxy, aryloxy or heteroaryloxy, substituted aryloxy or heteroaryloxy or a group xe2x80x94CH2xe2x80x94Oxe2x80x94Nxe2x95x90C(R16)R17, especially fluorine, chlorine and halo-C1-C3alkoxy;
R15 is halogen, C1-C8alkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C8alkoxy, C1-C4alkoxy-C1-C4alkyl or halo-C1-C8alkoxy, especially fluorine;
with the proviso that, if (R14)c is 4-chloro, 2-fluoro-4-[2-chloro-4-(trifluoromethyl)phenoxy] or 3,5-dichloro-4-[2-chloro-4-(trifluoromethyl)phenoxy], (R15)d is not 2,6-difluoro;
R16 and R17 independently of one another are C1-C4alkyl, C3-C6cycloalkyl or aryl, which are unsubstituted or substituted; in free form or in salt form;
of the formula
in which
e is 0, 1, 2 or 3, and R31 are identical or different if e is greater than 1,
R30 is C1-C8alkyl, phenyl-C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, aryl, heteroaryl or substituted aryl or heteroaryl, especially trifluoromethyl;
R31 is halogen, hydroxyl, cyano, nitro, C1-C8alkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C8alkoxy, C1-C4alkoxy-C1-C4alkyl or halo-C1-C8alkoxy or C1-C8alkylthio, especially chlorine or trifluoromethyl;
R32 and R33 independently of one another are hydrogen, C1-C8alkyl, phenyl-C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, aryl, heteroaryl or substituted aryl or heteroaryl,
or R32 and R33 together are a group
f is 0, 1, 2 or 3, and R34 are identical or different if f is greater than 1;
R34 is halogen, hydroxyl, cyano, nitro, C1-C8alkyl, C3-C6cycloalkyl, halo-C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C8alkoxy, C1-C4alkoxy-C1-C4alkyl or halo-C1-C8alkoxy or C1-C8alkylthio, especially hydroxyl; in free form or in salt form;
(E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine (acetamiprid), in free form or in salt form;
1-tert-butyl-3-(2,6-diisopropyl-4-phenoxyphenyl)thiourea (diafenthiuron), in free form or in salt form; and
2,3,4,5-tetrahydro-3-oxo-4-[(pyridin-3-yl)methyleneamino]-6-methyl-1,2,4-triazine (pymetrozine), in free form or in salt form.
The pesticidally active compounds of the formulae (I) to (V) are preferred in their free form.
Unless otherwise defined, the general terms used hereinabove and hereinbelow have the meanings given hereinbelow.
Halogenxe2x80x94per se or as structural element of groups and compounds such as haloalkyl, haloalkenyl, haloalkoxy and haloalkylthioxe2x80x94is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, mainly fluorine on the one hand and chlorine on the other hand.
Carbon-containing groups and compounds contain, unless otherwise defined, in each case 1 up to and including 9, preferably 1 up to and including 6, preferably 1 up to and including 4, in particular 1 or 2, carbon atoms.
Alkylxe2x80x94as a group per se and as structural element of other groups and compounds such as haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, dialkylaminocarbonyl, alkylcarbonyl and alkoxycarbonylxe2x80x94is, in each case with due consideration of the specific number of carbon atoms in the group or compound in question, is either straight-chain, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or nonyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isooctyl.
In phenylalkyl, an alkyl group bonded to the remaining moiety of the compound I is substituted by a phenyl group, the alkyl group preferably being straight-chain and the phenyl group preferably being bonded in a position higher than the xcex1-position, in particular in the xcfx89-position, of the alkyl group; examples are benzyl, 2-phenyl ethyl and 4-phenylbutyl.
Alkoxyhydroxyalkyl is an alkyl group which is substituted not only by one or more alkoxy groups, but also by one or more hydroxyl groups. Preferred is an alkyl group which is substituted by one alkoxy and one hydroxyl group.
Alkenyl, haloalkenyl, alkenyloxy, alkynyl, haloalkynyl and alkynyloxy are straight-chain or branched and contain in each case two or, preferably, one unsaturated carbon-carbon bond(s). The double or triple bonds of these substituents are preferably separated from the remaining moiety of the compound of the formula I by at least one saturated carbon atom. Examples which may be mentioned are allyl, methallyl, but-2-en-1-yl, but-3-en-2-yl, propargyl, but-2-yn-1-yl and but-3-yn-1-yloxy.
Halogen-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkenyl, haloalkoxy and haloalkylthio, can be partially halogenated or perhalogenated, in the case of polyhalogenation it being possible for the halogen substituents to be identical or different. Examples of haloalkylxe2x80x94as a group per se and as structural element of other groups and compounds such as haloalkoxy and haloalkylthio,xe2x80x94are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF2, CF2Cl, CFCl2 or CF3; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCl3, CF2CHCl2, CF2CHF2, CF2CFCl2, CF2CHBr2, CF2CHClF, CF2CF2Br, CF2CHBrF or CClFCHClF; propyl or isopropyl, mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3, CF2CF2CF3 or CH(CF3)2; and butyl or one of its isomers, mono- to nonasubstituted by fluorine, chlorine and/or bromine, such as CF(CF3)CHFCF3, CF2(CF2)2CF3 or CH2(CF2)2CF3. Haloalkyl R1 is preferably exclusively fluorinated, in particular perfluorinated. Examples of haloalkenyl are 2-chloroprop-2-en-1-yl, 2,3-dichloroprop-2-en-1-yl and 2,3-dibromoprop-2-en-1-yl.
Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferred is cyclopropyl.
Suitable hetero atoms in the ring skeleton of the heterocyclic radical are all elements of the Periodic Table which can form at least two covalent bonds.
Aryl is phenyl or naphthyl, especially phenyl. Heteroaryl is a five- or 6-membered heterocyclic aromatic radical which contains one or two hetero atoms selected from the group consisting of N, O and S. Preferred radicals b in the compounds of the formula (III) are those which contain one N atom, one N and one S atom or one O atom, especially pyridyl, thiazolyl and tetrahydrofuranyl.
Preferred active substances in the compositions according to the invention are the compounds of the formula (I); especially preferably a composition which comprises a compound of the formula (I) in which
a and b are O; or
X is O; or
A is C1-C6alkyl which is substituted by C1-C6alkoxy, xe2x80x94Oxe2x80x94Nxe2x95x90CH2, xe2x80x94Oxe2x80x94Nxe2x95x90CHxe2x80x94C1-C6alkyl, phenoxy, pyridyl, pyridyloxy, or is C2-C6alkenyl or C3-C6alkynyl; or in which
A is a radical of the formula (Ia), and R3 is C1-C6alkyl and R4 is hydrogen or C1-C3alkyl and R5 is hydrogen; or in which
A is a radical of the formula (Ib), and R6 is C1-C6alkyl or C1-C6alkoxy, R7 is hydrogen and Y is O.
Equally preferred as active substances in the compositions according to the invention are the compounds of the formula (II).
Preferred pesticidally active individual compounds which may be mentioned are:
4-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl phenyl ether, very especially a mixture of 50 to 80% of (2RS,4SR) 4-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl phenyl ether and 50 to 20% of (2RS,4RS) 4-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl phenyl ether (diofenolan);
3-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl fluorophenyl ether;
ethyl 2-(4-phenoxyphenoxy)ethylcarbamate (fenoxycarb);
4-phenoxyphenyl (R,S)-2-(pyridyloxy)propyl ether (pyriproxyfen);
N-tert-butyl-Nxe2x80x2-(4-ethylbenzoyl)-3,5-dimethylbenzohydrazide (tebufenozide);
N-tert-butyl-Nxe2x80x2-benzoylbenzohydrazide (RH 5849);
RH 2485, of the formula,
(methoxyfenozide);
ANS 1182;
isopropyl (E,E)-(R,S)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoate (methoprene);
prop-2-ynyl (xc2x1) (E,E)-3,7,11-trimethyidodeca-2,4-dienoate (kinoprene);
(E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine (NI-25, acetamiprid);
(xc2x1)-5-amino-1-(2,6-dichloro-xcex1xcex1xcex1-trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile (fipronil);
(R,S)-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-3-(2,6-difluorobenzoyl)-urea (lufenuron);
5-[(4-hydroxyphenyl)methyleneamino]-1-(2,6-dichloro-xcex1xcex1xcex1-trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile (vaniliprole);
(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine (imidacloprid);
(E)-N-(2-chlorothiazol-5-ylmethyl)-N-ethyl-Nxe2x80x2-methyl-2-nitrovinylidenediamine;
(E)-N-(2-chlorothiazol-5-ylmethyl)-N-methyl-Nxe2x80x2-methyl-2-nitrovinylidenediamine;
(E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-Nxe2x80x2-cyclopropyl-2-nitrovinylidenediamine;
(E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-Nxe2x80x2-ethyl-2-nitrovinylidenediamine;
(E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-Nxe2x80x2-methyl-2-nitrovinylidenediamine (nitenpyram);
(E)-N-(6-chloro-3-pyridylmethyl)-N-methyl-Nxe2x80x2-methyl-2-nitrovinylidenediamine;
(E)-N-(6-chloro-3-pyridylmethyl)-N-cyclopropyl-Nxe2x80x2-methyl-2-nitrovinylidenediamine;
(2-chloropyrid-5-ylmethyl)-3-methyl-4-nitroiminoperhydro-1,3,5-oxadiazine;
(2,3-dichloropyrid-5-ylmethyl)-3-methyl-4-nitroiminoperhydro-1,3,5-oxadiazine;
(2-chloropyrid-5-ylmethyl)-3-ethyl-4-nitroiminoperhydro-1,3,5-oxadiazine;
(2-chloropyrid-5-ylmethyl)-3-cyclopropylyl-4-nitroiminoperhydro-1,3,5-oxadiazine;
(2-chorothiazol-5-ylmethyl)-3-methyl-4-nitrolminoperhydro-1,3,5-oxadiazine;
(2-chlorothiazol-5-ylmethyl)-3-ethyl-4-nitroiminoperhydro-1,3,5-oxadiazine;
(2-chlorothiazol-5-ylmethyl)-3-cyclopropyl-4-nitroiminoperhydro-1,3,5-oxadiazine;
3-methyl-4-nitroimino-5-(1-oxido-3-pyridiniomethyl)perhydro-1,3,5-oxadiazine;
(2-chloro-1-oxido-5-pyridiniomethyl)-3-methyl-4-nitroiminoperhydro-1,3,5-oxadiazine; and
3-methyl-5-(2-methylpyrid-5-ylmethyl)-4-nitroiminoperhydro-1,3,5-oxadiazine.
Especially preferred as pesticidally active compounds for the purposes of the present invention are tebufenozide, diofenolan, fenoxycarb, methoprene, kinoprene and pyriproxyfen. Fenoxycarb is very especially preferred.
The compounds of the formulae (I) to (V) are known to those skilled in the art. In particular,
acetamiprid is known from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 730;
diafenthiuron from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 294;
diofenolan from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 363;
3-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl fluorophenyl ether;
fenoxycarb from The Pesticide Manual, 9thEd. (1991), The British Crop Protection Council, London, page 375;
fipronil from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 463;
imidacloprid from The Pesticide Manual, 9thEd. (1991), The British Crop Protection Council, London, page 491;
kinoprene from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 1102;
lufenuron from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 628;
methoprene from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 680;
nitenpyram from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 736;
pymetrozine from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 868;
pyriproxyfen from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 887;
RH 5849 from Brighton Crop Protection Conference, 1996, p. 481-486; and
tebufenozide from The Pesticide Manual, 10thEd. (1994), The British Crop Protection Council, London, page 943.
Surprisingly, it has now been found that the present compositions are outstandingly suitable for controlling pests, preferably for controlling eggs and larvae, in particular for controlling the eggs of the above pests, while having a good long-term action, being well tolerated by plants and leaving beneficial animals to a high degree unharmed. Application of the abovementioned signal substances or attractants allows considerably lesser amounts of insecticides, which are frequently toxic to warm-blooded species and beneficial animals, to be used when treating the cultivated areas to be protected. This novel procedure, which is advantageous from the ecological point of view, belongs to the principles of integrated crop protection. This is especially important since, normally, especially high amounts of pesticides must be used for controlling the eggs of pests. In particular, the finding is extremely surprising since the male insects are first attracted by the composition according to the invention which comprises the signal substance(s) and the pesticidally active compound(s), thus taking up the pesticide, and then transfer this pesticide to the female pests, from which it comes into contact with the eggs. It is as yet unknown whether the egg which has been deposited is already contaminated with the active ingredient or whether it comes into contact with the pesticide only after deposition, by means of contact with the female. Apart from this, the process is entirely novel; the possibility of controlling pests, especially their eggs, via this route has as yet not been recognized and opens up novel routes of pest control. The method of controlling pests via this route is therefore termed xe2x80x9cattract-and-sterilizexe2x80x9d method, in contrast to the xe2x80x9cattract-and-killxe2x80x9d method disclosed in, for example, EP-A-376,888. In the method according to the invention, the males are not destroyed, which is in contrast to the xe2x80x9cattract-and-killxe2x80x9d method. Nor must the effect be mistaken for the known systemic control of ectoparasites, in particular fleas, in domestic animals and productive livestock. In this last-mentioned method, the pesticidally active compound is administered to the host organismxe2x80x94for examplexe2x80x94together with the feed, the pesticide reaches the bloodstream of the host organism and is taken up from the female fleas directly from the blood.
A further important advantage of the application of the compositions according to the invention is the fact that they are active independently of whether the pest population to be controlled consists mainly of females or mainly of males, or whether they are approximately equal in number. This is not the case in the abovementioned xe2x80x9cattract-and-killxe2x80x9d method. If, when applying the last-mentioned method, the majority of animals in the population are females, it will be relatively highly probable that the males, which are in the minority, will find one of these females instead of a drop of the pesticidally active agent, and the result will be egg deposition by females which have not taken up pesticide via the males, which means that reproduction takes place. At first, this is also the case in the xe2x80x9cattract-and-sterilizexe2x80x9d method. However, since the females which have mated no longer give off pheromone and the males which have come into contact with the pheromone are not destroyed, the number of males in the population will in any case exceed the number of females after a very short time, so that the vast majority of females which mate from this point in time on will come into contact with the pesticidally active substance.
The compositions according to the invention are employed for controlling plants-injurious insects in crops of useful plants, afforestations and stands of ornamentals, in cotton, in fruit production and viticulture, in arable crops and in forestry, preferably in fruit production. The compositions are distinguished by a pronounced activity, in particular against larvae and eggs, mainly against eggs.
Furthermore, the compositions according to the invention can also be used for controlling ectoparasitic insects, for example Lucilia sericata, and representatives of the order Acarina, mainly ticks such as Boophilus microplus, which are injurious to productive livestock and domestic animals, for example by treating the animal houses and the grazing land.
Successful control within the scope of the subject of the invention is possible, in particular, of pests from the orders Lepidoptera, Coleoptera, Orthoptera, Isoptera, Psocoptera, Anoplura, Mallophaga, Thysanoptera, Heteroptera, Homoptera, Hymenoptera, Diptera, Siphonaptera, Thysanura and Acarina, mainly Lepidoptera and Coleoptera. Very especially good control is possible of the following pests:
Abagrotis spp., Abraxas spp., Acantholeucania spp., Acanthoplusia spp., Acarus spp., Acarus siro, Aceria spp., Aceria sheldoni, Acleris spp., Acoloithus spp., Acompsia spp., Acossus spp., Acria spp., Acrobasis spp., Acrocercops spp., Acrolepia spp., Acrolepiopsis spp., Acronicta spp., Acropolitis spp., Actebia spp., Aculus spp., Aculus schlechtendali, Adoxophyes spp., Adoxophyes reticulana, Aedes spp., Aegeria spp., Aethes spp., Agapeta spp., Agonopterix spp., Agriopis spp., Agriotes spp., Agriphila spp., Agrochola spp., Agroperina spp., Alabama ssp., Alabama argillaceae, Agrotis spp., Albuna spp., Alcathoe spp., Alcis spp., Aleimma spp., Aletia spp., Aleurothrixus spp., Aleurothrixus floccosus, Aleyrodes spp., Aleyrodes brassicae, Allophyes spp., Alsophila spp., Amata spp., Amathes spp., Amblyomma spp., Amblyptilia spp., Ammoconia spp., Amorbia spp., Amphion spp., Amphipoea spp., Amphipyra spp., Amyelois spp., Anacamptodes spp., Anagrapha spp., Anarsia spp., Anatrychyntis spp., Anavitrinelia spp., Ancylis spp., Andropolia spp., Anhimella spp., Antheraea spp., Antherigona spp., Antherigona soccata, Anthonomus ssp., Anthonomus grandis, Anticarsia spp., Anticarsia gemmatalis, Aonidiella spp., Apamea spp., Aphania spp., Aphelia spp., Aphididae, Aphis spp., Apotomis spp., Aproaerema spp., Archippus spp., Archips spp., Acromyrrnex, Arctia spp., Argas spp., Argolamprotes spp., Argyresthia spp., Argyrogramma spp., Argyroploce spp., Argyrotaenia spp., Arotrophora spp., Ascotis spp., Aspidiotus spp., Aspilapteryx spp., Asthenoptycha spp., Aterpia spp., Athetis spp., Atomaria spp., Atomaria linearis, Atta spp., Atypha spp., Autographa spp., Axylia spp., Bactra spp., Barbara spp., Batrachedra spp., Battaristis spp., Bembecia spp., Bemisia spp., Bemisia tabaci, Bibio spp., Bibio hortulanis, Bisigna spp., Blastesthia spp., Blatta spp., Blatella spp., Blepharosis spp., Bleptina spp., Boarmia spp., Bombyx spp., Bomolocha spp., Boophilus spp., Brachmia spp., Bradina spp., Brevipalpus spp., Brithys spp., Bryobia spp., Bryobia praetiosa, Bryotropha spp., Bupalus spp., Busseola spp., Busseola fusca, Cabera spp., Cacoecimorpha spp., Cadra spp., Cadra cautella, Caenurgina spp., Calipitrimerus spp., Callierges spp., Callophpora spp., Callophpora erythrocephala, Calophasia spp., Caloptilia spp., Calybites spp., Capnoptycha spp., Capua spp., Caradrina spp., Caripeta spp., Camienta spp., Carposina spp., Carposina nipponensis, Catamacta spp., Catelaphris spp., Catoptria spp., Caustoloma spp., Celaena spp., Celypha spp., Cenopis spp., Cephus spp., Ceramica spp., Cerapteryx spp., Ceratitis spp, Ceratophyllus spp., Ceroplaster spp., Chaetocnema spp., Chaetocnema tibialis, Chamaesphecia spp., Charanvca spp., Cheimophila spp., Chersotis spp., Chiasmia spp., Chilo spp., Chionodes spp., Chorioptes spp., Choristoneura spp., Chrysaspidia spp., Chrysodeixis spp., Chrysomya spp., Chrysomphalus spp., Chrysomphalus dictyospermi, Chrysomphalus aonidium, Chrysoteuchia spp., Cilix spp., Cimex spp., Clysia spp., Clysia ambiguella, Clepsis spp., Cnaemidophorus spp., Cnaphalocrocis spp., Cnephasia spp., Coccus spp., Coccus hesperidum, Cochylis spp., Coleophora spp., Colotois spp., Commophila spp., Conistra spp., Conopomorpha spp., Corcyra spp., Comutiplusia spp., Cosmia spp., Cosmopolites spp., Cosmopterix spp., Cossus spp., Costaeonvexa spp., Crambus spp., Creatonotos spp., Crocidolomia spp., Crocidolomia binotalis, Croesia spp., Crymodes spp., Cryptaspasma spp., Cryptoblabes spp., Cryptocala spp., Cryptophlebia spp., Cryptophlebia leucotreta, Cryptoptila spp., Ctenopseustis spp., Cucullia spp., Curculio spp., Culex spp., Cuterebra spp., Cydia spp., Cydia pomoneila, Cymbalophora spp., Dactylethra spp., Dacus spp., Dadica spp., Damalinea spp., Dasychira spp., Decadarchis spp., Decodes spp., Deilephila spp., Deltodes spp., Dendrolimus spp., Depressaria spp., Dermestes spp., Dermanyssus spp., Dermanyssus gallinae, Diabrotica spp., Diachrysia spp., Diaphania spp., Diarsia spp., Diasemia spp., Diatraea spp., Diceratura spp., Dichomeris spp., Dichrocrocis spp., Dichrorampha spp., Dicycla spp., Dioryctria spp., Diparopsis spp., Diparopsis castanea, Dipleurina spp., Diprion spp., Diprionidae, Discestra spp., Distantiella spp., Distantiella theobroma, Ditula spp., Diumea spp., Doratopteryx spp., Drepana spp., Drosphila spp., Drosphila melanogaster, Dysauxes spp., Dysdercus spp., Dysstroma spp., Eana spp., Eafias spp., Ecclitica spp., Ecdytolopha spp., Ecpyrrhorrhoe spp., Ectomyelois spp., Eetropis spp., Egira spp., Elasmopalpus spp., Emmelia spp., mpoasca spp., Empyreuma spp., Enargia spp., Enarmonia spp., Endopiza spp., Endothenia spp., Endotricha spp., Eoreuma spp., Eotetranychus spp., Eotetranychus carpini, Epagoge spp., Epelis spp., Ephestia spp., Ephestiodes spp., Epiblema spp., Epiehofistodes spp., Epinotia spp., Epiphyas spp., Epiplema spp., Epipsestis spp., Epirrhoe spp., Episimus spp., Epitymbia spp., Epilachna spp., Erannis spp., Erastria spp., Eremnus spp., Ereunetis spp., Eriophyes spp., Eriosoma spp., Eriosoma lanigerum, Erythroneura spp., Estigmene spp., Ethmia spp., Etiella spp., Euagrotis spp., Eucosma spp., Euehlaena spp., Euelidia spp., Eueosma spp., Euchistus spp., Eucosmomorpha spp., Eudonia spp., Eufidonia spp., Euhyponomeutoides spp., Eulepitodes spp., Eulia spp., Eulithis spp., Eupithecia spp., Euplexia spp., Eupoecilia spp., Eupoecilia ambiguella, Euproctis spp., Eupsilia spp., Eurhodope spp., Eurois spp., Eurygaster spp., Eurythmia spp., Eustrotia spp., Euxoa spp., Euzophera spp., Evergestis spp., Evippe spp., Exartema spp., Fannia spp., Faronta spp., Feltia spp., Filatima spp., Fishia spp., Frankliniella spp., Fumibotys spp., Gaesa spp., Gasgardia spp., Gastrophilus spp., Gelechia spp., Gilpinia spp., Gilpinia polytoma, Glossina spp., Glyphipterix spp., Glyphodes spp., Gnorimoschemini spp., Gonodonta spp., Gortyna spp., Gracillaria spp., Graphania spp., Grapholita spp., Grapholitha spp., Gravitarmata spp., Gretchena spp., Griselda spp., Gryllotalpa spp., Gynaephora spp., Gypsonoma spp., Hada spp., Haematopinus spp., Halisidota spp., Harpipteryx spp., Harrisina spp., Hedya spp., Helicoverpa spp., Heliophobus spp., Heliothis spp., Hellula spp., Helotropa spp., Hemaris spp., Hercinothrips spp., Herculia spp., Hermonassa spp., Heterogenea spp., Holomelina spp., Homadaula spp., Homoeosoma spp., Homoglaea spp., Homohadena spp., Homona spp., Homonopsis spp., Hoplocampa spp., Hoplodrina spp., Hoshinoa spp., Hxalomma spp., Hydraecia spp., Hydriomena spp., Hyles spp., Hyloicus spp., Hypagyrtis spp., Hypatima spp., Hyphantria spp., Hyphantria cunea, Hypocala spp., Hypocoena spp., Hypodema spp., Hyppobosca spp., Hypsipyla spp., Hyssia spp., Hysterosia spp., Idaea spp., Idia spp., Ipimorpha spp., Isia spp., Isochorista spp., Isophrictis spp., Isopolia spp., Isotrias spp., Ixodes spp., Itame spp., Jodia spp., Jodis spp., Kawabea spp., Keiferia spp., Keiferia lycopersicella, Labdia spp., Lacinipolia spp., Lambdina spp., Lamprothritpa spp., Laodelphax spp., Lasius spp., Laspeyresia spp., Leptinotarsa spp., Leptinotarsa decemlineata, Leptocorsa spp., Leptostales spp., Lecanium spp., Lecanium comi, Lepidosaphes spp., Lepisma spp., Lepisma saccharina, Lesmone spp., Leucania spp., Leucinodes spp., Leucophaea spp., Leucophaea maderae, Leucoptera spp., Leucoptera scitella, Linognathus spp., Liposcelis spp., Ussorhoptuis spp., Lithacodia spp., Lithocolletis spp., Lithomoia spp., Uthophane spp., Lixodessa spp., Lobesia spp., Lobesia botrana, Lobophora spp., Locusta spp., Lomanaltes spp., Lomographa spp., Loxagrotis spp., Loxostege spp., Lucilia spp., Lymantria spp., Lymnaecia spp., Lyonetia spp., Lyriomyza spp., Macdonnoughia spp., Macrauzata spp., Macronoctua spp., Macrosiphus spp., Malacosoma spp., Maliarpha spp., Mamestra spp., Mamestra brassicae, Manduca spp., Manduca sexta, Marasmia spp., Margaritia spp., Matratinea spp., Matsumuraeses spp., Melanagromyza spp., Melipotes spp., Melissopus spp., Melittia spp., Melolontha spp., Meristis spp., Meritastis spp., Merophyas spp., Mesapamea spp., Mesogona spp., Mesoleuca spp., Metanema spp., Metendothenia spp., Metzneria spp., Micardia spp., Microcorses spp., Microleon spp., Mnesictena.spp., Mocis spp., Monima spp., Monochroa spp., Monomorium spp., Monomorium pharaonis, Monopsis spp., Morrisonia spp., Musca spp., Mutuuraia spp., Myelois spp., Mythimna spp., Myzus spp., Naranga spp., Nedra spp., Nemapogon spp., Neodiprion spp., Neosphaleroptera spp., Nephelodes spp., Nephotettix spp., Nezara spp., Nilaparvata spp., Niphonympha spp., Nippoptilia spp., Noctua spp., Nola spp., Notocelia spp., Notodonta spp., Nudaurelia spp., Ochropleura spp., Ocnerostoma spp., Oestrus spp., Olethreutes spp., Oligia spp., Olindia spp., Olygonychus spp., Olygonychus gallinae, Oncocnemis spp., Operophtera spp., Ophisma spp., Opogona spp., Oraesia spp., Omiodoros spp., Orgyia spp., Oria spp., Orseolia spp., Orthodes spp., Orthogonia spp., Orthosia spp., Oryzaephilus spp., Oscinella spp., Oscinella frit, Osminia spp., Ostrinia spp., Ostrinia nubilalis, Otiorhynchus spp., Ourapteryx spp., Pachetra spp., Pachysphinx spp., Pagyda spp., Paleacrita spp., Paliga spp., Paithis spp., Pammene spp., Pandemis spp., Panemeria spp., Panolis spp., Panolis flammea, Panonychus spp., Parargyresthia spp., Paradiarsia spp., Paralobesia spp., Paranthrene spp., Parapandemis spp., Parapediasia spp., Parastichtis spp., Parasyndemis spp., Paratoria spp., Pareromeme spp., Pectinophora spp., Pectinophora gossypiella, Pediculus spp., Pegomyia spp., Pegomyia hyoscyami, Pelochrista spp., Pennisetia spp., Penstemonia spp., Pemphigus spp., Peribatodes spp., Peridroma spp., Perileucoptera spp., Periplaneta spp., Perizoma spp., Petrova spp., Pexicopia spp., Phalonia spp., Phalonidia spp., Phaneta spp., Phlyctaenia spp., Phlyctinus spp., Phorbia spp., Phragmatobia spp., Phricanthes spp., Phthorimaea spp., Phthorimaea operculella, Phyllocnistis spp., Phyllocoptruta spp., Phyllocoptruta oleivora, Phyllonorycter spp., Phyllophila spp., Phylloxera spp., Pieris spp., Pieris rapae, Piesma spp., Planococus spp., Planotortrix spp., Platyedra spp., Platynota spp., Platyptilia spp., Platysenta spp., Plodia spp., Plusia spp., Plutella spp., Plutella xylostelia, Podosesia spp., Polia spp., Popillia spp., Polymixis spp., Polyphagotarsonemus spp., Polyphagotarsonemus latus, Prays spp., Prionoxystus spp., Probole spp., Proceras spp., Prochoerodes spp., Proeulia spp., Proschistis spp., Proselena spp., Proserpinus spp., Protagrotis spp., Proteoteras spp., Protobathra spp., Protoschinia spp., Pselnophorus spp., Pseudaletia spp., Pseudanthonomus spp., Pseudatemelia spp., Pseudaulacaspis spp., Pseudexentera spp., Pseudococus spp., Pseudohermenias spp., Pseudoplusia spp., Psoroptes spp., Psylta spp., Psylliodes spp., Pterophorus spp., Ptycholoma spp., Pulvinaria spp., Pulvinaria aethiopica, Pyralis spp., Pyrausta spp., Pyrgotis spp., Pyrreferra spp., Pyrrharctia spp., Quadraspidiotus spp., Rancora spp., Raphia spp., Reticultermes spp., Retinia spp., Rhagoletis spp, Rhagoletis pomonella, Rhipicephalus spp., Rhizoglyphus spp., Rhizopertha spp., Rhodnius spp., Rhophalosiphum spp., Rhopobota spp., Rhyacia spp., Rhyacionia spp., Rhynchopacha spp., Rhyzosthenes spp., Rivula spp., Rondotia spp., Rusidrina spp., Rynchaglaea spp., Sabulodes spp., Sahibergella spp., Sahlbergella singularis, Saissetia spp., Samia spp., Sannina spp., Sanninoidea spp., Saphoideus spp., Sarcoptes spp., Sathrobrota spp., Scarabeidae, Sceliodes spp., Schinia spp., Schistocerca spp., Schizaphis spp., Schizura spp., Schreckensteinia spp., Sciara spp., Scirpophaga spp., Scirthrips auranti, Scoparia spp., Scopula spp., Scotia spp., Scotinophara spp., Scotogramma spp., Scrobipalpa spp., Scrobipalpopsis spp., Semiothisa spp., Sereda spp., Sesamia spp., Sesia spp., Sicya spp., Sideridis spp., Simyra spp., Sineugraphe spp., Sitochroa spp., Sitobion spp., Sitophilus spp., Sitotroga spp., Solenopsis spp., Smerinthus spp., Sophronia spp., Spaelotis spp., Spargaloma spp., Sparganothis spp., Spatalistis spp., Sperchia spp., Sphecia spp., Sphinx spp., Spilonota spp., Spodoptera spp., Spodoptera littoralis, Stagmatophora spp., Staphylinochrous spp., Stathmopoda spp., Stenodes spp., Sterrha spp., Stomoxys spp., Strophedra spp., Sunira spp., Sutyna spp., Swammerdamia spp., Syllomatia spp., Sympistis spp., Synanthedon spp., Synaxis spp., Syncopacma spp., Syndemis spp., Syngrapha spp., Synthomeida spp., Tabanus spp., Taeniarchis spp., Taeniothrips spp., Tannia spp., Tarsonemus spp., Tegulifera spp., Tehama spp., Teleiodes spp., Telorta spp., Tenebrio spp., Tephrina spp., Teratoglaea spp., Terricula spp., Tethea spp., Tetranychus spp., Thalpophila spp., Thaumetopoea spp., Thiodia spp., Thrips spp., Thrips palmi, Thrips tabaci, Thyridopteryx spp., Thyris spp., Tineola spp., Tipula spp., Tortricidia spp., Tortrix spp., Trachea spp., Trialeurodes spp., Trialeurodes vaporariorum, Triatoma spp., Triaxomera spp., Tribolium spp., Tricodectes spp., Trichoplusia spp., Trichoplusia ni, Trichoptilus spp., Trioza spp., Trioza erytreae, Triphaenia spp., Triphosa spp., Trogoderma spp., Tyria spp., Udea spp., Unaspis spp., Unaspis citri, Utetheisa spp., Valeriodes spp., Vespa spp., Vespamima spp., Vitacea spp., Vitula spp., Witlesia spp., Xanthia spp., Xanthorhoe spp., Xanthotype spp., Xenomicta spp., Xenopsylla spp., Xenopsylla cheopsis, Xestia spp., Xylena spp., Xylomyges spp., Xyrosaris spp., Yponomeuta spp., Ypsolopha spp., Zale spp., Zanclognathus spp., Zeiraphera spp., Zenodoxus spp., Zeuzera spp., Zygaena spp.,
The good pesticidal activity of the compositions according to the invention correspond to a destruction rate (mortality) of at least 50-60% of the abovementioned pests, or of their eggs and larvae.
Behaviour-altering substances which are suitable for the invention are pheromones, kairomones and attractants, primarily pheromones. Such signal substances are effective even at extraordinarily low concentrations and are capable of altering the behaviour of the insects in a manner which allows their control. Pheromones are sexual signal substances produced in most cases by the female adults of the pests, primarily insects, which attract the male individuals of the same pest species. The natural pheromones are volatile and can display their attractant action over vast distances. The term xe2x80x9cpheromonexe2x80x9d may be used to describe not only a chemically defined individual compound, but also a mixture of compounds. It depends on the species whether it means a defined individual compound or a mixture of compounds. Suitable for the purposes of the invention are, in principle, all pheromones which have been described in the literature.
The compositions according to the invention comprise the behaviour-altering substance preferably in an amount of from 0.01 to 10% by weight, in particular 0.02 to 5% by weight, very especially 0.04 to 2%. Most especially preferred is a pheromone content of 0.08 to 0.24% by weight for controlling the eggs of representatives of the order Lepidoptera, and a pheromone content of from 0.7 to 0.9% by weight for controlling the eggs of representatives of the order Coleoptera. A typical pheromone content for controlling the eggs of representatives of the order Lepidoptera is 0.16% by weight, and for controlling the eggs of representatives of the order Coleoptera 0.8% by weight. Also preferred is a composition which comprises only one pheromone. In the case of kairomones and attractants, which are mostly used in compositions for controlling larval stages, amounts of from 0.5 to 30% by weight, especially 5 to 20% by weight, are employed.
Structure and composition of the pheromones are known from the literature. Examples of pheromones which can be used within the scope of the present invention are the following:
Z-5-decenyl acetate, dodecanyl acetate, Z-7-dodecenyl acetate, E-7-dodecenyl acetate, Z-8-dodecenyl acetate, E-8-dodecenyl acetate, Z-9-dodecenyl acetate, E-9-dodecenyl acetate, E-10-dodecenyl acetate, 11-dodecenyl acetate, Z-9,11-dodecadienyl acetate, E-9,11-dodecadienyl acetate, Z-11-tridecenyl acetate, E-11-tridecenyl acetate, tetradecanyl acetate, E-7-tetradecenyl acetate, Z-8-tetradecenyl acetate, E-8-tetradecenyl acetate, Z-9-tetradecenyl acetate, E-9-tetradecenyl acetate, Z-10-tetradecenyl acetate, E-10-tetradecenyl acetate, Z-11-tetradecenyl acetate, E-11-tetradecenyl acetate, Z-12-pentadecenyl acetate, E-12-pentadecenyl acetate, hexadecanyl acetate, Z-7-hexadecenyl acetate, Z-11-hexadecenyl acetate, E-11-hexadecenyl acetate, octadecanyl acetate, E,Z-7,9-dodecadienyl acetate, Z,E-7,9-dodecadienyl acetate, E,E-7,9-dodecadienyl acetate, Z,Z-7,9-dodecadienyl acetate, E,E-8,10-dodecadienyl acetate, E,Z-9,12-dodecadienyl acetate, E,Z-4,7-tridecadienyl acetate, 4-methoxy-cinnamaldehyde-xcex2-ionone, estragol (4-allylanisole), eugenol (4-allyl-2-methoxyphenol), indole, 8-methyl-2-decyl propanoate, E,E-9,11-tetradecadienyl acetate, Z,Z-9,12-tetra-decadienyl acetate, Z,Z-7,11-hexadecadienyl acetate, E,Z-7,11-hexadecadienyl acetate, Z,E-7,11-hexadecadienyl acetate, E,E-7,11-hexadecadienyl acetate, Z,E-3,13-octadecadienyl acetate, E,Z-3,13-octadecadienyl acetate, E,E-3,13-octadecadienyl acetate, ethanol, hexanol, heptanol, octanol, decanol, Z-6-nonenol, E-6-nonenol, dodecanol, 11-dodecenol, Z-7-dodecenol, E-7-dodecenol, Z-8-dodecenol, E-8-dodecenol, E-9-dodecenol, Z-9-dodecenol, E-9,11-dodecadienol, Z-9,11-dodecadienol, Z,E-5,7-dodecadienol, E,E-5,7-dodecadienol, E,E-8,10-dodecadien-1-ol (codlemone, codlure), E,Z-8,10-dodecadienol, Z,Z-8,10-dodecadienol, Z,E-8,10-dodecadienol, E,Z-7,9-dodecadienol, Z,Z-7,9-dodecadienol, E-5-tetradecenol, Z-8-tetradecenol, Z-9-tetradecenol, E-9-tetradecenol, Z-10-tetradecenol, Z-11-tetradecenol, E-11-tetradecenol, Z-11-hexadecenol, Z,E-9,11-tetradecadienol, Z,E-9,12-tetradecadienol, Z,Z-9,12-tetradecadienol, Z,Z-10,12-tetradecadienol, Z,Z-7,11-hexadecadienol, Z, E-7,11-hexadecadienol, (E)-14-methyl-8-hexadecen-1-ol, (Z)-14-methyl-8-hexadecen-1-ol, E,E-10,12-hexadecadienol, E,Z-10,12-hexadecadienol, dodecanal, Z-9-dodecenal tetradecanal, Z-7-tetradecenal, Z-9-tetradecenal, Z-11-tetradecenal, E-11-tetradecenal, E-11,13-tetradecadienal, E,E-8,10-tetradecadienal, Z,E-9,11-tetradecadienal, Z,E-9,12-tetradecadienal hexadecanal, Z-8-hexadecenal, Z-9-hexadecenal, Z-10-hexadecenal, E-10-hexadecenal, Z-11-hexadecenal, E-11-hexadecenal, Z-12-hexadecenal, Z-13-hexadecenal (Z)-14-methyl-8-hexadecenal (E)-14-methyl-8-hexadecenal-Z,Z-7,11-hexadecadienal, Z,E-7,11-hexadecadienal, Z,E-9,11-hexadecadienal, E,E-10,12-hexadecadienal, E,Z-10,12-hexadecadienal, Z,E-10,12-hexadecadienal, Z,Z-10,12-hexadecadienal, Z,Z-11,13-hexadecadienal octadecanal, Z-11-octadecenal, E-13-octadecenal, Z-13-octadecenal, Z-5-decenyl-3-methyl butanoate.
Kairomones are also naturally occurring signal substances. They are produced by plants and consist in most cases of a mixture of a multiplicity of various volatile odouriferous substances. The kairomones are capable of attracting insects and representatives of the order Acarina. However, repellent effects are also possible, depending on the concentration. The activity of the kairomones must be seen in context with the fact that insects and Acarina live in close symbiosis with the plants in question.
The so-called attractants are known chemical compounds which are relatively readily available and which are capable of affecting the behaviour of pests in the sense that the pests are made accessible and exposed in especially high degree to the action of pesticides which are simultaneously present.
Such kairomones and attractants, which can also be used for the purposes of the inventionxe2x80x94preferably in combination with pheromonesxe2x80x94are also known from the literature.
Naturally, the pesticidally active compounds employed in the compositions and products according to the invention must be compatible with the remaining constituents of the composition according to the invention and at least mostly soluble therein. Nor must the pesticidally active ingredients evaporate too rapidly; rather they must be present in or on the surface of the microdrop or drop-shaped zones for an adequate period so as to allow uptake of the active ingredient by the pest to be controlled. The compositions according to the invention preferably comprise 1 to 15% by weight, especially 5 to 12% by weight, of the pesticidally active compound. A typical content of pesticidally active compound is 10% by weight. Preferred is a composition which comprises only one pesticidally active compound.
A flowable composition for the purposes of the invention is a composition which typically shows flow characteristics like honey or glue, for example. Compositions with better flowability can be employed so long as they adhere well to the support, for example the leaf or the bark of the plant. The viscosity of the composition according to the invention is preferably within a range of from 1000 to 40 000, especially 10 000 to 30 000, in particular 15 000 to 25 000 cP (centipoise). A typical viscosity is 20 000 cP.
The viscosities of the compositions according to the invention are normally determined using a method in which the torque required to overcome the resistance of a fluid, due to its viscosity, to the rotatory movement of a cylinder or disc is measured by means of the tension of a metal spring (so-called torsion principle). The tension of the spring shown (torque) is proportional to the viscosity, which is given in millipascal seconds (mPa s=1 cP). The measurements are carried out for example using a Brookfield Synchro-Lectric viscometer, model LV, from Brookfield Engineering Laboratories Inc., Stoughton, Mass., USA.
The term UV absorber is to be understood as meaning, in accordance with the invention, a compound which has a main absorption range of between 200 and 450 nm, especially between 270 and 400 nm. In most cases, these are the known commercially available UV absorbers which are known in particular from the plastics industry. Compounds which are preferably employed are those belonging to the following classes of substances: benzotriazole derivatives, benzophenone derivatives, cinnamic acid derivatives, oxalanilides, sterically hindered amines, in particular piperidine derivatives, and triazines. The benzotriazole derivatives are especially preferred. If appropriate, other substances which are not normally termed UV absorbers in the narrow sense may be used for this purpose provided they are sufficiently stable to light, have a sufficiently high absorption in the abovementioned absorption range and are capable of being processed together with the remaining components to give a composition with the desired viscosity. Sterically hindered amines, especially piperidine derivatives, are mentioned in the present context amongst the UV absorbers even though their mode of action is probably due to their antioxidant characteristics. In the event that they are employed, they are preferably not employed alone, but in combination with one or more substances from one of the other classes of UV absorbers mentioned, especially in combination with benzotriazoles, preferably in an amount of 5 to 10% by weight relative to the entire composition.
Especially preferred is a composition which comprises 50 to 95% by weight, especially 60 to 90%, in particular 70 to 90%, especially preferably 80 to 90%, of the UV absorber or UV absorber mixture known per se. A typical content is 85% by weight. Also preferred is a composition which comprises only one UV absorber. Preferably used are liquid or flowable UV absorbers with a cP value of between 1000 and 40 000, especially between 10 000 and 30 000. On the other hand, it is also possible to use one or more solid UV absorbers and to convert them, with or without other auxiliaries, for example solvents, into the desired flowable form. It is also possible to mix a flowable UV absorber with a solid UV absorberxe2x80x94again, with or without further auxiliariesxe2x80x94to convert the composition into the desired flowable form.
Examples of sub-groups of UV absorbers and free-radical scavengers of the abovementioned classes which are especially suitable in accordance with the invention are:
A) 2-(2-Hydroxyphenyl)benzotriazoles of the formula
in which R51 is H or halogen, especially H or Cl; very especially H or 5xe2x80x94Cl
R52 is H, C1-C18alkyl, phenyl-C1-C12alkyl, phenyl; especially C1-C12alkyl,
R53 is H, C1-C18alkyl, phenyl-C1-C12alkyl, phenyl, xe2x80x94(CH2)gxe2x80x94COOxe2x80x94C1-C12alkyl, xe2x80x94(CH2)hxe2x80x94COOxe2x80x94C1-C24alkenyl; and
g and h independently of one another are 1 to 20, especially 2; or
R53 is a chain formed by reacting a compound of the formula (VI), in which R53 is a radical xe2x80x94(CH2)gxe2x80x94COOxe2x80x94C1xe2x80x94C12alkyl with a polyethyleneglycol.
Especially preferred compounds of the formula (VI) are:
the reaction product of
and HO(CH2CH2O)iH
(polyethylene glycol 300, i=6 or 7, mean molecular weight of the reaction product greater than 600, known under the tradename Tinuvin 1130);
the reaction product formed by alkylating 2-(2-hydroxy-5-methylphenyl)benzotriazole with i-dodecene:
2-(2xe2x80x2-hydroxy-3xe2x80x2-tert-butyl-5xe2x80x2-methylphenyl)-5-chlorobenzotriazole (Tinuvin 326);
2-(2xe2x80x2-hydroxy-3xe2x80x2,5xe2x80x2-di-tert-butylphenyl)-5-chlorobenzotriazole (Tinuvin 327);
2-(2xe2x80x2-hydroxy-3xe2x80x2,5xe2x80x2-di-tert-amylphenyl)benzotriazole (Tinuvin 328);
2-(2xe2x80x2-hydroxy-3xe2x80x2,5xe2x80x2-di-tert-butylphenyl)-5-chlorobenzotriazole (Tinuvin 329); and
the compound of the formula
in which Ra is
C4-C18alkyl, especially C8alkyl, very especially a compound in which Ra is composed of approximately 50% n-octyl and approximately 50% 2-ethylhexyl (Tinuvin 109);
B) 2-hydroxy-4-alkoxybenzophenones of the formula
in which
R54=H, C1-C18alkyl, C1-C18alkoxy
R55=C1-C18alkyl, preferably xe2x80x94C8H17 and xe2x80x94C12H25,
especially the compound of the formula (VII), in which R54 is hydrogen and xe2x80x94OR55 is 4-O-n-C8H17 (Chimassorb 81);
C) oxalanilides of the formula
in which
R56 is C1-C18alkyl and
R57 is C1-C18alkyl;
D) cinnamic acid derivatives of the formula
in which
R58 is H or C1-C18alkyl;
R59 is H or C1-C6alkyl or phenyl;
R60 is H or C1-C18alkoxy and
R61 is H, CN or COO-C1-C18alkyl;
in free form or in salt form;
E) triazine derivatives of the formula
in which
R62 and R64 independently of one another are H, C1-C12alkyl or OH;
R63 and R65 independently of one another are C1-C18alkyl or C1-C18alkoxy;
R66 is C1-C18alkyl; C1-C18alkoxy-C1-C12alkyl, C1-C18alkoxyhydroxy-C1-C12alkyl;
k is 0, 1 or 2 and
l is 0, 1 or 2;
where, if k and/or l are 2, the radicals R63 and R65 are independent of one another;
in free form or in salt form;
especially a mixture of 2-[4-((2-hydroxy-3-didecyloxypropyl)-oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-((2-hydroxy-3-tridecyloxypropyl)-oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, with an approximate molecular weight of 654 (Tinuvin 400);
F) piperidine derivatives of the formula
in which the radicals R70 independently of one another are hydrogen or C1-C4alkyl, especially hydrogen or methyl, and
m is 2 to 8, especially 8,
in free form or in salt form;
especially bis-2,2,6,6-tetramethyl-4-piperidyl sebacate (Tinuvin 770 DF) and bis-1,2,2,6,6-pentamethyl-4-piperidyl sebacate (Tinuvin 765);
G) piperidine derivatives of the formula
in which the radicals R71 independently of one another are hydrogen or C1-C4alkyl, especially hydrogen or methyl,
AA and BB independently of one another are C1-C8alkylene, especially xe2x80x94CH2xe2x80x94CH2xe2x80x94, and
n is sufficiently large that the molecular weight of the compound is between 1000 and 4000;
in free form or in salt form;
especially poly-(N-xcex2-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidyl succinate (Tinuvin 622 LD);
and the compounds n-butylamine-nickel 2,2xe2x80x2-thiobis(4-tert-octylphenolate) (Chimassorb N-705), and
poly-{[6-[(1,1,3,3-tetramethylbutyl)imino]-1,3,5-triazine-2,4-diyl][2-(2,2,6,6-tetramethylpiperidyl)amino]hexamethylene-[4-(2,2,6,6-tetramethylpiperidyl)imino]} (Chimassorb 944 LD/FL).
If required, the flowable products according to the invention may comprise customary viscosity-regulating thickeners in an amount of from 1 to 47% by weight, preferably in an amount of from 1 to 20% by weight. Examples of suitable organic thickeners are: base-neutralized acrylic acid polymers of high molecular weight and relatively high viscosity (xe2x80x9cCarbpolexe2x80x9d types), polyvinylpyrrolidones, cellulose gums, in particular cellulose alkyl esters and cellulose alkyl ethers (xe2x80x9cBlanosexe2x80x9d types), liquid polyalkylene glycol block copolymers of ethylene oxide and propylene oxide (xe2x80x9cPluronicxe2x80x9d types), polyethylene glycols with a molecular weight of above 10 000, and polyisobutylene with a molecular weight of approximately 1000 (Glissopal 1000). Amongst the inorganic thickeners, the following may be mentioned, for example: precipitated or pyrogenic silicas, aluminas and rock meals, in particular calcite, various types of talcum, or kaolins, bentonites, montmorillonites, smectites and attapulgite, aluminalsilica (xe2x80x9cAerosilxe2x80x9d types) and sodium aluminium silicates. Quartz sand or crosslinked solid pulverulent polymers may be incorporated into the products as additional fillers.
To modify the viscosity of the flowable products according to the invention, it may be expedient in certain cases to add an inert solvent or diluent. These solvents should be compatible with the remaining constituents of the product and, preferably, of low volatility. Suitable examples are the following solvents: ethers and ether-like compounds of low volatility such as dipropyl ether, dibutyl ether, dioxane, dimethoxyethane and tetrahydrofuran; N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, in particular pentanes, hexanes, heptanes, octanes, hexadecane, toluene, xylenes, chlorohydrocarbons and chlorobenzenes, alcohols, such as ethanol, propanols, t-butanol and higher alcohols; nitriles, such as acetonitrile or propionitrile; and ketones, for example methyl isopropyl ketone and methyl isobutyl ketone; alkyl esters of aliphatic carboxylic acids, such as butyl propionate, methyl oxalate, dibutyl sebacate, di(2-ethylhexyl) sebacate. In general, the formulations according to the invention only comprise relatively small amounts of solvents, for example 1 to 2% by weight.
If required, the compositions according to the invention can furthermore comprise other formulation auxiliaries which serve to adapt the composition to specific conditions or which protect the biological active ingredients which they comprise against certain environmental factors. Such formulation auxiliaries can be substances which provide an additional protection against UV, such as finely divided carbon powders (e.g. pigment-grade carbon black), dyes and colour pigments (e.g. Sudan black, Chromophthal blue, Terasil blue, Cibacet yellow, titanium dioxide, zinc sulfate and zinc oxides), optical brighteners (e.g. Uvitex or Tinopal DMS), antioxidants (e.g. butylhydroxytoluene or 2,6-di-tert-butyl-p-cresol) and, in some cases, also specific surfactants and emulsifiers (e.g. anionic surfactants: sodium lauryl sulfate, calcium dodecylbenzenesulfonate, and non-ionic surfactants: fatty alcohol ethoxylates, alkylphenol ethoxylates, oleyl alcohol ethoxylates, ethylene oxide/propylene oxide block copolymers, fatty amine ethoxylates, silicone surfactants). Lime pigments and colour pigments may amount to 1 to 20% by weight, preferably 3 to 10% by weight, of the compositions according to the invention, optical brighteners to 0.1 to 2% by weight, antioxidants to 0.1 to 5% by weight, and surfactants and emulsifiers to 0.1 to 1% by weight.
Within the scope of the method according to the invention for controlling plant-injurious insects and representatives of the order Acarina, the compositions according to the invention are generally not distributed over the agriculturally cultivated area by using conventional devices as they are known to the expert, since said conventional methods ire more suitable for spraying compositions of low viscosity, for example aqueous emulsions or suspensions. Rather, methods which have proved successful are, for example, automatic pipettes with suitable dosing devices by means of which individual microdrops or drop-shaped zones are applied. Also suitable are devices with intermittent drop delivery which is controlled by pressurized air or mechanically, and these devices are mainly suitable for larger areas. The microdrops are applied directly to the plants or to a suitable location in the vicinity of the plants, preferably to the plants, for example to the leaves or bark, preferably to the leaves. The number of microdrops or drop-shaped zones distributed over the cultivated area to be treated may differ within the scope of the present invention, depending on the species of the pests to be controlled and their developmental stages. 50 up to 100 000 microdrops or drop-shaped zones may be distributed per 1000 m2 of the cultivateded area to be protected, and 100 to 1500, especially 200 to 500, microdrops or drop-shaped zones of the composition according to the invention are generally distributed. The size of the microdrops applied is preferably 5 to 3000 xcexcl, in particular 30 to 1000 xcexcl, especially 30 to 200 xcexcl, typically 50 xcexcl.
In the following examples which illustrate the invention, parts and percentages are by weight, unless stated otherwise:

Abstract: which composition comprises 40 to 98% by weight of the UV absorber or the UV absorber mixture,

Abstract: 0.01 to 30% by weight of one or more signal substance(s) and

Abstract: 0.1 to 20% by weight of one or more pesticidally active compound(s) of the formulae (I) to (V) as specified, and a method of controlling harmful insects and representatives of the order Acarina using this composition.