JPH07163240A - Tree-protection method - Google Patents

Abstract

PURPOSE:To surely and effectively protect a tree by introducing a solid composition composed of a tree-protecting active compound, etc., into the region of the sap-passing vessel of the tree. CONSTITUTION:A tree is protected by mixing (A) one or more kinds of tree- protecting active compounds selected from 0, 0-dimethyl-0-3- methyl-4-(methylsulfinyl) phenyl phosphorothioate, trans-1, 4, 5, 6- tetrahydro-1-methyl-2-[ 2-(3-methyl-2thienyl) vinyl]pyrimidine tartaric acid salt, (-)-(S)-2, 3, 5, 6-tetrahydro-6-phenylimida [2,l-b]thiazole hydrochloride and 1-(6- chloro-3-pyridylmethyl)-N-nitro-imidazolidin-2-ylidenamine with (B) a carrier such as a polymeric carrier e.g. a polymer decomposable by microorganisms (e.g. starch polymer) and introducing the obtained solid composition into a region of the sap-passing vessel of the tree.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for protecting trees.

[0002]

BACKGROUND OF THE INVENTION It is already known to inject stems of deciduous or coniferous trees with solutions of certain insecticides or to embed powdered formulations ("Chemicals, Abstracts" CA 108: 181188w; CA9
9: 83692v; CA 99: 181184; CA
87: 146712). The above method is limited only to the application of the readily water-soluble active compound having a penetrating effect. When the method is carried out under actual working conditions, i.e. the application method in which a suitable amount of active compound is introduced into the sap stream to minimize damage to the plant, only a few types of plants are tested. Even if it is done for the purpose of, only an insufficient effect can be obtained.

It is already known to embed active compounds in polymeric matrices so that the active compounds are slowly released from the matrix. Such sustained release solid form treating agents have been used to release active compounds into soil over a relatively long period of time ("Chemicals, Abstracts" CA 100: 47099n,
And U.S. Pat. No. 3,269,900). Also, another type of polymer / active compound-containing formulation has been used to release readily volatile active compounds homogeneously into the atmosphere over a relatively long period of time (US Pat. No. 3,3,3).
18,764). Yet another class of polymer / active compound containing formulations has been used to protect animals from parasite damage. In this case, the active compound transferred to the surface of the polymer is the animal's coat.
Are mechanically scraped by and distributed in the body of animals (US Pat. No. 3,852,416).

The active compound is applied in the form of a suitable formulation in such a way that it is distributed over the surface of the plant as much as possible by the usual operations of atomizing, spraying, dusting and the like. It therefore comes into direct contact with the plant pests to be controlled.
Alternatively, it must be able to penetrate the protective layer of the plant and reach the point of action through the flow of sap in the plant. These treatment methods are associated with a great loss of active compound. Also, in the method comprising applying the active compound to the root part of the plant and absorbing the active compound from the root part to reach the point of action through the sap flow, the same as in the case described above. Can be said. Furthermore, when the active compound is applied to the root part, it must be present in the soil in a sufficiently high concentration so that the plant can absorb it sufficiently. In order to adjust the application rate of the active compound as precisely as possible to the amount of active compound actually required by the plant, it is desirable to introduce said required amount of active compound directly into the sap stream in the plant. In this case, however, the plants (eg the useful productive fruit trees (eg useful productive fruit trees) are applied even after several applications.
There is a precondition that it must not damage ve fruit trees). Further, in recent years, for the control of pine wood nematodes, which is the main cause of pine wilting with increasing damage, control of pine wood nematode, which is a vector of pine wood nematode by air spray of insecticide, and pine wood nematode itself. The control by ampoule injection of a drug to the tree trunk is actively carried out.

[0005]

[Means for Solving the Problems]
Succeeded in finding a new tree protection method. That is, a method for protecting trees by introducing a solid form composition obtained by mixing a tree protecting active compound and a carrier into the area of the sap-conducting path of trees. Furthermore, the solid form tree-protecting active composition obtained by mixing the tree-protecting active compound and the carrier exhibits a strong controlling effect against tree pests. Accordingly, the present invention relates to tree protection methods and compositions for use therein. The method of the present invention is a very suitable method for the protection of individual useful trees.

Examples of the tree-protecting active compound in the present invention include all active compounds for the purpose of protecting trees, and particularly, insecticidal compounds and bactericidal compounds. And as a suitable insecticidal compound, O,
O-dimethyl O-3-methyl-4- (methylsulfinyl) phenyl phosphorothioate, trans-1,
4,5,6-Tetrahydro-1-methyl-2- [2-
(3-Methyl-2-thienyl) vinyl] pyrimidine tartrate, (−)-(s) -2,3,5,6-tetrahydro-6-phenylimida [2,1-b] thiazole hydrochloride, 1- ( 6-chloro-3-pyridylmethyl) -N-nitro-imidazolidine-2-ylideneamine and the like can be exemplified.

The above insecticidal compound can be mixed with a bactericidal compound for controlling tree diseases. Examples of these fungicidal compounds include sulfenamides such as dichlorfluanid (Eupalene), tolylfluanid (Methyleupalene), phorpet and fluorophorpet; benzimidazoles such as carbendazim (MBC), benomyl, fuveridazole, thiabendazole. Or salts thereof; thiocyanates such as thiocyanatomethylthiobenzothiazole (TCMTB) and methylenebisthiocyanate (MBT); quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyl-dimethyl-dodecylammonium chloride and dodecyl-dimethylammonium chloride. Morpholine derivatives such as C ₁₁
-C _{14-4-alkyl-2,6-dimethyl} - morpholine homologues (tridemorph), (±) -cis-4- [3-
t-Butylphenyl) -2-methylpropyl] -2,6
-Dimethylmorpholine (fenpropimorph) and farimorph;

Phenols such as o-phenylphenol, tribromophenol, tetrachlorophenol, pentachlorophenol, 3-methyl-4-chlorophenol, di-chlorophene, chlorphene or salts thereof; azoles such as triadimefon, triadimenol, Bitertanol, tebuconazole, propiconazole, azaconazole, hexaconazole, prochloraz, cyproconazole, 1- (2-chlorophenyl)
-2- (1-chlorocyclopropyl) -3- (1,2,
4-triazol-1-yl) -propan-2-ol and 1- (2-chlorophenyl) -2- (1,2,4)
-Triazol-1-yl-methyl) -3,3-dimethyl-butan-2-ol. Iodopropargyl derivative,
For example, iodopropargyl butyl-carbamate (I
PBC), chlorophenylformal, phenylcarbamate, hexylcarbamate and cyclohexylcarbamate, and iodopropargyloxyethylphenylcarbamate;

Iodine derivatives such as diiodomethyl-p
-Aryl-sulfones, such as diiodomethyl-p-
Tolyl-sulfone; Bromine derivative such as bromopol; Isothiazoline such as N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-Dichloro-N-octyl-isothiazoline-3- On, N-octylisothiazoline-3
-One (onthirinone); benzisothiazolinone and cyclopentene-isothiazoline; pyridines such as 1-hydroxy-2-pyridinethione and tetrachloro-4-methylsulfonylpyridine;

Nitriles, such as 2,4,5,6-tetrachloroisophthalonitrile (chlortalonyl),
And a fungicide having an active halogen group, for example Cl-
Examples include Ac, MCA, tectamer, bromopol and bromidox; benzothiazoles such as 2-mercaptobenzothiazole; dicarboximides such as iprodione, vinclozolin, procymidone; dazomet; and quinolines such as 8-hydroxyquinoline. Further, the above bactericidal compounds can be used alone in carrying out the present invention. Examples of trees that can be mentioned as objects of tree protection of the present invention include pine species (red pine, black pine, spruce pine, todomatsu, larch, German spruce, etc.), beech species (beech, chestnut, chestnut, oak, etc.), cedar species. (Japanese cedar, sawara, cypress, etc.) can be exemplified.

Examples of pests relevant to the present invention include tree pest insects and nematodes, and also fungi and bacteria. Examples of harmful insects include Coleoptera, for example, Cerambycidae, Beetles, Weevil, Scarabaeidae, Chrysomelidae: Hymenoptera, for example, Hymenoptera, Haboptera: Diptera, for example, Thysanoptera: Hemiptera,
For example, aphids, psyllids, scale insects, hagolomosas, stink beetles, stink bugs: Lepidoptera, for example, beetles, beetles, rhododendrons, beetle bugs, leaf beetles, mosquito bugs, boktoga,
Bats: pine wood nematode (Bursaph)
elenchus xylophilus Nickl
e) etc. can be mentioned.

Further, examples of fungi and bacteria include:
All tree diseases can be mentioned, and in general, Plasmodiophoromyces
ets), Oomycetes, and Chitridiomycete
s), Zygomycetes, Ascomycetes, Basidiomycetes, and various plant diseases caused by Deuteromycetes, and the Pseudomonas family (Pseudomoseos).
nadaceae), Rhizobidae (Rhizobia
ceae), Enterobacteriaceae (Enteroba)
cteriaceae), Corynebacterium family (Co
Various plant diseases caused by Rynebacterium and Streptomycetes can be mentioned.

The solid form composition in the present invention is a rod-shaped material, a cylindrical material, a shell-shaped material, a nail-shaped material, a bone-nail-shaped material, a spike,
It can be used in the form of plugs, needles, hollow nails, flakes, clamps (pins), and wires. These can be drilled and embedded in the hole, forcedly inserted or pressed into the soft tissue of the plant, or tapped, or the rubbery bark of bark that has been carefully peeled or lifted. It can be pushed underneath the part and then covered in place with the exfoliated bark. Particularly preferred examples of the method for applying the tangible article or solid form composition described above include the use of commercially available nailing or tacking devices, such as those using compressed air, for the tangible article or solid form treatment. Applying the agent can be mentioned.

Examples of the carrier in the present invention include polymeric carriers. The example is as follows. All polymers which can be used for the production of plastics molding compositions, such as polyolefins such as polyethylene, polyisobutylene and polypropylene; vinyl polymers such as polyvinyl chloride (PVC), polyvinyl acetate, polyvinyl alcohol, polystyrene and polyacrylonitrile; polyacrylates. And polymethacrylates; polyacetals; polycondensates and polyadducts such as polyamides, polyesters, polyurethanes, polycarbonates and polyalkylene terephthalates; polyaryl ethers and polyimides; polyalkylene oxide alkyl and alkyl aryl ethers; and high molecular weight polyalkylene oxides, such as Homo- and copolymers of ethylene oxide and propylene oxide.

Further polymers which may be mentioned are olefin / vinyl ester copolymers, eg ethylene / vinyl acetate copolymers; ethylene / vinyl alcohol copolymers; olefin / acrylate and methacrylate copolymers, eg ethylene / acrylic acid copolymers,
Ethylene / ethyl acrylate copolymers and ethylene / methyl acrylate copolymers; and ABS copolymers, styrene / acrylonitrile copolymers, styrene / butadiene copolymers, and olefin / maleic anhydride copolymers such as ethylene / maleic anhydride copolymers.

Further polymeric carrier materials which can be used are: Starch polymers, such as natural starch, amylose and starch polymer / thermoplastic mixtures,
Sugar polymers such as polymaltose; and cellulose and cellulose derivatives such as cellulose esters, cellulose ethers and cellulose nitrates. Polyoxyalkylated cellulose, starch and lignin sulfonate. Hydrogels such as alginate. Natural resins such as colophony, gum arabic and agar agar.

Further polymeric carrier materials which may be mentioned are thermoplastic elastomers. These are materials which have an elastomeric phase physically incorporated or chemically bonded to a polymer which can be processed as a thermoplastic. There is a difference between polyblends in which the elastomeric phase is present in a physically mixed form and block copolymers in which the elastomeric phase is a component of the polymeric matrix. As a result of constructing a thermoplastic elastomer, hard and soft regions are present side by side. The hard regions here form a crystalline network structure or a continuous phase, the intermediate spaces of which are filled with elastomer segments. Due to this construction, these materials have rubber-like properties.

There are differences mainly among the five groups of thermoplastic elastomers which may be mentioned as suitable in this respect: Copolyester 2. Polyether block amide (PEBA) 3. Thermoplastic polyurethane (TPU) 4. Thermoplastic polyolefin (TPO) 5. Styrene block copolymer. Of course, mixtures of the above polymers can also be used as the polymeric carrier material. Suitable polymeric carrier materials can be processed as thermoplastics and have a softening point of 50 to 260 ° C, particularly preferably 50 to 200 ° C. Also suitable are polymers that are degradable via photochemical processes, such as ethylene / CO 2 copolymers, vinyl ketone copolymers and polymers containing additives that initiate photodegradation.

Particularly suitable polymers are biodegradable polymers such as starch polymers and starch polymer / thermoplastic mixtures; sugar polymers; celluloses and cellulose derivatives; polyoxyalkylated celluloses and starches; hydrogels such as alginates; natural resins such as Colophony, gum arabic and agar
Agar; from homo- and copolymers of lactic acid, such as polylactide and polylactide glycolide, and polyglycolide. Poly-ε-caprolactone, and polyhydroxyalkanoates such as poly-3-hydroxybutyric acid (PHB) and 3-
Hydroxybutyric acid and 3-hydroxyvaleric acid (PHB
Polymers selected from the group consisting of copolymers with V) are particularly suitable. The plasticizers commonly used for plasticizing solid vinyl resins are suitable for the production of shaped articles based on polymers which can be treated as thermoplastics (for example polyvinyl resins). The plasticizer used depends on the resin and its compatibility with the plasticizer. Examples of suitable plasticizers are esters of phosphoric acid such as tricresyl phosphate, esters of phthalic acid such as dimethyl phthalate and dioctyl phthalate, and esters of adipic acid such as diisobutyl adipate. Still other esters such as esters of azelaic acid, maleic acid, ricinoleic acid, myristic acid, palmitic acid, oleic acid, sebacic acid, stearic acid and trimellitic acid, as well as complex linear polyesters, polymeric plasticizers and epoxides. Soybean oil can also be used. The amount of plasticizer is about 10-50 based on the weight of the total composition.
% By weight, preferably about 20-45% by weight.

In addition, the shaped articles can also include components such as stabilizers, lubricants, fillers, surfactants and colorants without changing the basic properties of the composition. Suitable stabilizers are antioxidants and agents that protect the molded article from UV irradiation and undesired deterioration during processing such as extrusion. Stabilizers such as epoxidized soybean oil also act as secondary plasticizers. Lubricants that can be used include stearates,
Stearic acid and low molecular weight polyethylene. These components can be used in concentrations of up to 20% by weight, based on the total composition. Polymers selected from the group of particularly suitable polycondensates are polyamides and / or polyesters, which have a melting or softening point between 50 and 160 ° C. Among the types of polyamide, preferred are ω-aminocaproic acid, ω-aminoenanthyl acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocaprylic acid, ω-aminoundecylic acid, ω-amino. Lauric acid and / or caprolactam, lactam-7, lactam-8, lactam-9, lactam-10, lactam-11
Or lauryllactam and / or dimethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, polyether-diamine and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberin Homopolyamides and / or copolyamides of acids, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid and dimerized fatty acids.

Caprolactam, lauryllactam, ω-
Aminolauric acid, ω-aminocaproic acid, hexamethylenediamine, polyether-diamine, adipic acid,
Particularly preferred are dimerized fatty acids or mixtures thereof. Among the types of polyester, ω-hydroxyacetic acid, ω
-Hydroxypropionic acid, ω-hydroxybutyric acid, ω-
Hydroxyvaleric acid, ω-hydroxycaproic acid, ω
-Hydroxyenanthylic acid, ω-hydroxycaprylic acid, ω-hydroxypelargonic acid, ω-hydroxycapric acid, ω-hydroxyundecyl acid, ω-hydroxylauric acid and / or caprolactone, lactone-
7, lactone-8, lactone-9, lactone-10, lactone-11, lauryl lactone and / or ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, aliphatic diol having 2 to 18 carbon atoms Mixtures, as well as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid Homopolyesters and / or copolyesters of acids and / or their anhydrides and / or their chlorides and / or their esters are preferred.

Polyurethanes are prepared by reacting polyisocyanates with higher molecular weight compounds having at least two groups reactive towards isocyanates and optionally low molecular weight chain extenders and / or monofunctional chain terminators. It is produced by a method known per se [eg S. H.
Sounders, K. C. Fries, polyurethane,
Part I, High Polymer Science XVI, Interscience Publishers Publishing, New York (196
2)]. The preferred polyisocyanates are generally toluylene diisocyanate and diphenylmethane diisocyanate. Of course, it is also possible to use mixtures of the abovementioned compounds having at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight of 400 to 10000, for example mixtures of polyethers and polyesters. Further possible starting components which may optionally be used are compounds having at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight of 32 to 400.
In this case, this is understood to mean compounds having hydroxyl and / or amino and / or thiol and / or carboxyl groups, preferably compounds having hydroxyl and / or amino groups, which are chain extenders or Acts as a cross-linking agent.
In general, these compounds have 2 to 8 hydrogen atoms, preferably 2 or 3 reactive hydrogen atoms, which are reactive towards isocyanates. Photodegradable polymers are polymers that contain groups sensitive to UV light and / or additives that initiate photochemical reactions.

Polymers having groups sensitive to UV light which may be mentioned are, for example, US Pat. No. 2,495,286 and German Patents 2 316 697 and 39.
No. 21 144, a copolymer of ethylene and carbon monoxide produced by free radical polymerization.
For example, US Pat. Nos. 3,759,952 and 3811.
No. 931, No. 385 814, No. 3 860 53
No. 8 and No. 3878 169 vinyl monomers having a keto group (for example, methyl vinyl ketone,
Mention may further be made of copolymers of methyl isopropenyl ketone and ethyl vinyl ketone) with for example polyolefins (eg ethylene, propylene) and vinyl compounds (eg styrene and methyl methacrylate). Products of this kind are available, for example, under the name Ecolite® and can be used as polymeric carrier materials by themselves or preferably in admixture with the corresponding base polymers in amounts of 5 to 10 parts by weight. . Polymers containing additives as photodegradation initiators are preferably, for example, polyethylene, polybut-1.
Made based on polyolefins such as ene and vinyl resins, eg polystyrene and PVC.
The photoreactive additives are preferably organic carbonyl compounds such as aromatic aldehydes, ketones, diketones and quinones. Benzophenone and its derivatives are particularly preferred. Another group of suitable photoreactive additives are inorganic and organic salts, for example chlorides of transition metals such as iron, nickel, cobalt, copper and manganese, stearates and octanoates. Organic complexes of transition metals such as ferrocene and preferably dithiocarbamates of iron and magnesium are also used.

Of the starch polymers, starch and starch polymer / thermoplastic mixtures which can be treated as thermoplastics are particularly suitable as polymeric carrier materials. They can be used as such and / or as masterbatches mixed with thermoplastics. The thermoplastic preferably comprises an amount of photodegradable polymer. Starch that can be processed as a thermoplastic is, for example, EP-0 118 240.
Starch containing water as a softening agent as described in No.
For example, EP-0304 401 and 0 391
Degraded starches as described in 853; and hydroxyalkoxylated starches such as hydroxyethyl- and hydroxypropyl-substituted starches. Starches with a high amylose content containing softeners can also be processed as thermoplastics, as described, for example, in DE-A-4 013 344. Suitable softeners are polyhydric alcohols such as glycerin, diethylene glycol, triethylene glycol, sorbitol, polyvinyl alcohol and citric oxide adducts.

The starch polymer / thermoplastic mixture contains a mixture of 6 to 15 parts by weight of starch and, for example, PVC, ethylene / vinyl acetate copolymer, polyurethane and preferably polyolefins such as polypropylene, particularly preferably polyethylene. It is available under the names Ecostar, Polyclean, Amiplast and Poly-grade. The starch used for this kind of mixture with thermoplastics can be surface-modified, for example with silanes, or it can be used in the dry state as unmodified starch. These mixtures can also contain additives. For example, these are unsaturated compounds such as unsaturated fatty acid esters such as soybean oil; styrene / butadiene block copolymers; natural rubber; as well as organic salts of transition metals such as cobalt naphthenate, as well as antioxidants of the known type.
Starch polymer / thermoplastic mixtures which have a starch content of up to 95% by weight and are obtained, for example, by mixing starch with polymers having carboxyl groups (for example ethylene / acrylic acid copolymers) can also be used according to the invention. .

The preparation of these mixtures from degraded starch is described, for example, in EP-0 404 727. E
P-0 519 367 is used to mix starch chemically modified by the reaction of OH groups with alkylene oxides and other substances forming ethers, esters, urethanes, carbamates and / or isocyanates with thermoplastics. . Copolyamides, copolyesters and / or polyolefins are preferred. Polyols as softeners such as glycerin, sorbitol and polyethylene glycol, urea and / or urea derivatives, and emulsifiers such as metal stearates, glycerin monostearate and polyoxyethylene fatty acid esters such as polyoxyethylene-
20 sorbitan monolaurate can also be added to these mixtures. The starch polymer / thermoplastic mixtures which can be used according to the invention further comprise graft copolymers of starch with maleic anhydride and vinyl monomers such as styrene, acrylonitrile, and acrylic and methacrylic monomers such as butyl and methyl methacrylate as compatibilizers. It can also be included. Also suitable are copolymers such as those obtained according to German Patent No. 3 007 433 by polymerizing ethylene in the presence of starch modified with a Ziegler-Natta catalyst.

Cellulose and cellulose derivatives such as cellulose esters such as cellulose acetate, cellulose propionate, cellulose butyrate, and mixed esters such as cellulose acetobutyrate; cellulose ethers such as methyl-, ethyl- and hydroxyethyl cellulose and sodium carboxy. Methylcellulose and also cellulose nitrate are known and suitable as polymeric carrier materials. Suitable substances are derivatives which can be treated as thermoplastics and / or are degradable, for example the cellulose esters described in EP-0 394 803 (eg cellulose acetate and / or
Or a mixture of cellulose acetobutyrate) and a biodegradable additive (eg a carboxylic acid ester having several ester groups and / or hydroxyl groups, eg an ester of citric acid, tartaric acid or succinic acid) as a softening agent, wire An organic acid and / or acid ester different from the polyester and, if necessary, a softening agent. For example, iron (II) acetylacetonate or bis (cyclopentadienyl) -iron or its derivatives,
It can be included in the mixture to further increase the degradability.

A particularly suitable polymeric carrier material is a cellulose / lactone graft copolymer, for example cellulose polyhydroxyhexanoate. Polyhydroxyalkanoates are polymers of aliphatic and aromatic hydroxycarboxylic acids produced by prokaryotic microorganisms, eg EP-0 015669, 0 046.
It can be produced by a fermentation method as described in No. 344 and No. 052 459. Suitable polyhydroxyalkanoates are, for example, 4-hydroxybutyric acid,
4-hydroxyvaleric acid and 5-hydroxyvaleric acid; for example, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, 4-methylhexanoic acid, 5- Methyl hexanoic acid, 5-methyl octanoic acid, 6
3-Hydroxy derivatives of saturated carboxylic acids such as-methyloctanoic acid and 7-methyloctanoic acid; eg protic acid, 4-pentenoic acid, 4-hexenoic acid, 5-hexenoic acid, 6-octenoic acid, 7-octenoic acid. 3-hydroxy derivatives of unsaturated carboxylic acids such as, 8-nonenoic acid, 9-decenoic acid, 6-dodecenoic acid, 5-tetradecenoic acid and 5,8-tetradecadienoic acid; and for example 6-
3-Hydroxy derivatives of halogenocarboxylic acids such as bromohexanoic acid, 6-chlorohexanoic acid, 7-fluoroheptanoic acid, 8-bromooctanoic acid, 8-chlorooctanoic acid, 9-fluorononanoic acid and 11-bromoundecanoic acid. Is a polymer of.

Suitable polymeric carrier materials are homo- and copolymers of 3-hydroxybutyric acid, copolymers of which with 3-hydroxyvaleric acid are particularly preferred. Products of this kind are available, for example, under the name Biopol®. Examples of the carrier include the followings in addition to the polymeric carrier. Solid fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid; solid fats such as waxes such as spermaceti and carnauba wax; paraffin waxes; solid surfactants such as polyalkylene oxide alkyls or Alkyl aryl ether, polyalkylene oxide fatty acid ester, polyalkylene oxide alkyl ester, polyalkylene oxide alkyl amine, poly fatty acid ester, polyalkylene oxide polyol ester ether, alkyl sulfonate, alkyl aryl sulfonate, alkyl naphthalene sulfonate,
Dialkyl sulfosuccinates, polyalkylene alkyl ether sulphates, polyalkylene oxide alkyl ether phosphonates, polyalkylene oxide alkyl aryl ether phosphonates and polyol phosphonates.

The fillers and additives optionally contained in the polymeric carrier material are substances known per se, such as inorganic or organic based fillers and short fibers, colorants such as dyes and color pigments, water binders, It should be understood to mean a surface-active solid substance or a pH stabilizer.
Examples of inorganic fillers include barita, titanium dioxide,
Quartz sand, kaolin, carbon black and glass microbeads. Among the organic fillers, it is possible to use polymers based on polystyrene or polyvinyl chloride, for example. Possible short fibers are, for example, 0.1 to 1 m long
m glass fibers or fibers of organic origin such as polyester fibers or polyamide fibers. To give the polymeric carrier material the desired color, organic or inorganic based dyes or color pigments which are known per se for coloring polymers, for example iron oxide pigments or chromium oxide pigments or phthalocyanine- or monoazo-tea pigments are used. Can be used. The preferred water binder is zeolite. Solid surface-active substances which may be mentioned are, for example, cellulose powder, activated carbon, silicic acid preparations and chrysotile asbestos.

In order to produce a molded article according to the present invention, the respective components are mixed in a dry state by a known mixing method, and a known extrusion method, injection molding method, compression molding method (tabletting method) or melt molding method. Can be molded by. It is also possible to mix the individual components by dissolving the individual components in a common solvent and then precipitating the mixture in a suitable non-solvent. In this method, the solution is forcibly introduced into the precipitation bath, preferably through a die, and the agglomerates formed are drawn out as filaments (wet spinning method). Precipitation is preferably carried out by known dry and wet spinning processes. The choice of processing method for producing the shaped article according to the invention depends, principally industrially, on the rheological properties of the shaped article material and the shape of the desired structure. The processing method can be adjusted according to the processing technique or according to the type of molding.
In the case of processing techniques, these methods can be classified according to the rheological conditions which they pass through. Therefore casting, pressing, spraying and spreading are suitable for viscous molded article materials, injection molding for viscoelastic polymers,
Extrusion, calendering, milling and optionally kneading are suitable. Classified according to the type of molding, the molded articles according to the invention can be produced by casting, dipping, compression molding, injection molding, extrusion calendering, embossing, bending, deep drawing, spinning and the like. These processing methods are known,
No more detailed explanation is needed. Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these.

[0032]

【Example】

Compound A: O, O-dimethyl O-3-methyl-4-
(Methylsulfinyl) phenyl phosphorothioate compound B: trans-1,4,5,6-tetrahydro-
1-methyl-2- [2- (3-methyl-2-thienyl)
Vinyl] pyrimidine tartrate compound C: (−)-(s) -2,3,5,6-tetrahydro-6-phenylimidazole [2,1-b] thiazole hydrochloride compound D: 1- (6-chloro-3 -Pyridylmethyl)-
N-nitro-imidazolidine-2-ylideneamine

Formulation Example 1 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Crystalline cellulose 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 2 Composition% by weight Compound B 80.0 Synthetic amorphous silica 6.8 Calcium stearate 0.2 Crystalline cellulose 13.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation example 3 Composition% by weight Compound C 80.0 Synthetic amorphous silica 6.8 Calcium stearate 0.2 Crystalline cellulose 13.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 4 Composition Wt.% Compound D 70.0% Polyethylene glycol 29.0% Calcium stearate 1.0% Tablet-molded into a shape with a diameter of 6 mm and a length of 40 mm. Formulation Example 5 Composition% by weight Compound D 70.0% Polyethylene glycol 29.0% Calcium stearate 1.0% Tablet-molded to give a product having a diameter of 9 mm and a length of 20 mm.

Formulation Example 6 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polycarboxylic acid 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 7 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyethylene oxide 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 8 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polypropylene oxide 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 9 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyethylene polypropylene copolymer 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 10 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Starch 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm.

Formulation Example 11 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Amylose 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 12 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polymaltose 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 13 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Cellulose 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 14 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Carboxymethylcellulose 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 15 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Hydroxypropylcellulose 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm.

Formulation Example 16 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Hydroxyethyl cellulose 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 17 Composition wt% Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Methylcellulose 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 18 Composition wt% Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Ethylcellulose 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation example 19 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Lignin 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 20 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Sodium lignin sulfonate 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm.

Formulation Example 21 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Calcium lignin sulfonate 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation example 22 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Lignin sulfonic acid 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 23 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyalkylene oxide alkyl ether 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation example 24 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyalkylene oxide alkylaryl ether 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 25 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyalkylene oxide fatty acid ester 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm.

Formulation Example 26 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyalkylene oxide alkyl ester 44.0 Tablet-molded to obtain a product having a diameter of 6 mm and a length of 40 mm. . Formulation Example 27 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyalkylene oxide alkylamine 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation example 28 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Poly fatty acid ester 44.0 Tablet-molded to obtain a product having a diameter of 6 mm and a length of 40 mm. Formulation example 29 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyalkylene oxide polyol ester ether 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 30 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Alkyl sulfonate 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm.

Formulation Example 31 Composition wt% Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Alkylaryl sulfonate 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation example 32 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Alkylnaphthalene sulfonate 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 33 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Dialkylsulfosuccinate 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation Example 34 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyalkylene alkyl ether sulphate 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm. Formulation example 35 Composition wt% Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyalkylene oxide alkyl ether phosphonate 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm.

Formulation Example 36 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyalkylene oxide alkylaryl ether phosphonate 44.0 Tablet-molded, 6 mm in diameter and 40 mm in length And Formulation Example 37 Composition% by weight Compound A 50.0 Synthetic amorphous silica 5.8 Calcium stearate 0.2 Polyol phosphonate 44.0 Tablet-molded to give a product having a diameter of 6 mm and a length of 40 mm.

Test Example 1 Pine wilt prevention effect test I Method In the early summer (June), a 15-year-old black pine was prepared, and the above-mentioned formulation examples 1 and 2 were used.
A predetermined number of the shape compositions of 3 and 3 were embedded in the trunk of each pine tree. Use 5 pine trees per test plot. Approximately one month later, each pine was pierced with a total of 3 holes (4 mm in diameter and 1 cm in depth), 2 in the upper part and 1 in the main trunk, and about 15,000 pine / 0.1 ml pine nuts per hole. The nematode was inoculated. Before and 2 months after the inoculation, the state of the pine resin was evaluated by the resin evaluation method (Oda formula). The test result shows the average of 5 pine trees in one test section, and the result is shown in Table 1.

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[Table 1]

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[Table] Table 2 below shows the resin determination method (Oda's method) for pine trees.

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[Table 2]

Test Example 2 Pine wilt prevention effect test II Method In substantially the same manner as the method shown in Test Example 1, in the middle of April,
The shaped composition of Formulation Example 4 was treated. Then, about 3 months later, the pinewood nematode was similarly inoculated, and the resin state of the pine was similarly determined before the inoculation and 2 months after the inoculation. The test result shows the average value of 5 pine trees in one test section, and the result is shown in Table 2.

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[Table 3]

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EFFECTS OF THE INVENTION By using the method of the present invention, tree protection can be carried out accurately and effectively, and such a method is epoch-making.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location A01N 43/54 F 43/90 103 57/14 D (72) Inventor Shigeharu Koyama Oyamashi Station, Tochigi Prefecture 1-5-7 Minamimachi (72) Takehisa Abe 1-9-31 Wakagicho, Oyama City, Tochigi Prefecture

Claims (8)

[Claims] 1. A method for protecting trees, which comprises introducing a solid form composition obtained by mixing a tree protecting active compound and a carrier into the area of a tree sap passage. 2. The tree protecting method according to claim 1, wherein the tree protecting active compound is a pest controlling active compound. 3. The tree protecting method according to claim 1, wherein the tree protecting active compound is a pinewood nematode controlling agent. 4. A tree protecting active compound is O, O-dimethyl O-3-methyl-4- (methylsulfinyl) phenyl phosphorothioate, trans-1,4,5,6-tetrahydro-1-methyl-2- [ 2- (3-methyl-2-thienyl) vinyl] pyrimidine tartrate, (-)-(s) -2,3,5,6-tetrahydro-6-
The tree protection method according to claim 1, which is at least one selected from phenylimidazole [2,1-b] thiazole hydrochloride and 1- (6-chloro-3-pyridylmethyl) -N-nitro-imidazolidin-2-ylideneamine. . 5. The tree protecting method according to claim 1, wherein the carrier is a polymeric carrier. 6. A solid, tree-protecting active composition comprising a mixture of a tree-protecting active compound and a carrier. 7. The composition according to claim 6, wherein the tree-protecting active compound is a compound listed in claim 4. 8. The composition of claim 6, wherein the carrier is a polymeric carrier.