The invention relates to novel active combinations of certain cyclic ketoenols and certain insecticidally active compounds that together have good insecticidal and acaricidal properties.

The present invention relates to novel active compound combinations comprising known cyclic ketoenols on the one hand and other known insecticidally active compounds on the other hand and which are highly suitable for controlling animal pests such as insects and undesired acarids.
It is already known that certain cyclic ketoenols have insecticidal and acaricidal properties (EP-A-528 156). WO 95/01971, EP-A-647 637, WO 96/16061, WO 96/20196, WO 96/25395, WO 96/35664, WO 97/02243, WO 97/01535, WO 97/36868, WO 97/43275, WO 98/05638, WO 98/06721, WO 99/16748, WO 99/43649, WO 99/48869 and WO 99/55673 describe further ketoenols having insecticidal and acaricidal properties. The activity of these substances is good; however, at low application rates it is sometimes unsatisfactory.
Furthermore, it is already known that numerous heterocycles, organotin compounds, benzoylureas and pyrethroids have insecticidal and acaricidal properties (cf. WO 93/22 297, WO 93/10 083, DE-A-2 641 343, EP-A-347 488, EP-A-210 487, U.S. Pat. No. 3,264,177 and EP-A-234 045). However, the activity of these substances is not always satisfactory.
It has now been found that compounds of the formula (I)
in which
X represents C1-C6-alkyl, halogen, C1-C6-alkoxy or C1C3-halogenoalkyl,
Y represents hydrogen, C1-C6-alkyl, halogen, C1-C6-alkoxy or C1-C3-halogenoalkyl,
Z represents C1-C6-alkyl, halogen or C1-C6-alkoxy,
n represents a number from 0 to 3,
A represents hydrogen or in each case optionally halogen-substituted straight-chain or branched C1-C12-alkyl, C3-C8-alkenyl, C3-C8-alkinyl, C1-C10-alkoxy-C2-C8-alkyl, C1-C8-polyalkoxy-C2-C8-alkyl, C1-C10-alkylthio-C2-C8-alkyl or cycloalkyl having 3-8 ring atoms which may be interrupted by oxygen and/or sulphur and represents in each case optionally halogen-, C1-C6-alkyl-, C1-C6-halogenoalkyl-, C1-C6-alkoxy-, C1-C6-halogenoalkoxy- or nitro-substituted phenyl or phenyl-C1-C6-alkyl,
B represents hydrogen, C1-C6-alkyl or C1-C6-alkoxy-C2-C4-alkyl
or in which
A and B together with the carbon atom to which they are attached form a saturated or unsaturated 3- to 8-membered ring which is optionally interrupted by oxygen and/or sulphur and optionally substituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-halogenoalkyl, C1-C4-halogenoalkoxy, C1-C4-alkylthio or optionally substituted phenyl or is optionally benzo-fused,
G represents hydrogen (a) or represents a group
in which
R1 represents in each case optionally halogen-substituted C1-C20-alkyl, C2-C20-alkenyl, C1-C8-alkoxy-C2-C8-alkyl, C1-C8-alkylthio-C2-C8-alkyl, C1-C8-polyalkoxy-C2-C8-alkyl or cycloalkyl having 3-8 ring atoms which may be interrupted by oxygen and/or sulphur atoms,
represents optionally halogen-, nitro-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-halogenoalkyl- or C1-C6-halogenoalkoxy-substituted phenyl,
represents optionally halogen-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-halogenoalkyl- or C1-C6-halogenoalkoxy-substituted phenyl-C1-C6-alkyl,
represents in each case optionally halogen- and/or C1-C6-alkyl-substituted pyridyl, pyrimidyl, thiazolyl or pyrazolyl,
represents optionally halogen- and/or C1-C6-alkyl-substituted phenoxy-C1-C6-alkyl,
R2 represents in each case optionally halogen-substituted C1-C20-alkyl, C2-C20-alkenyl, C1-C8-alkoxy-C2-C8-alkyl or C1-C8-polyalkoxy-C2-C8-alkyl,
represents in each case optionally halogen-, nitro-, C1-C6-alkyl-, C1-C6-alkoxy- or C1-C6-halogenoalkyl-substituted phenyl or benzyl,
R3 represents optionally halogen-substituted C1-C8-alkyl, represents in each case optionally C1-C4-alkyl-, halogen-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-,C1-C4-halogenoalkoxy-, nitro- or cyano-substituted phenyl or benzyl,
R4 and R5 independently of one another represent in each case optionally halogen-substituted C1-C8-alkyl, C1-C8-alkoxy, C1-C8-alkylamino, di-(C1-C8)-alkyl-amino, C1-C8-alkylthio, C2-C5-alkenylthio, C2-C5-alkinylthio or C3-C7-cycloalkylthio, represent in each case optionally halogen-, nitro-, cyano-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogeno-alkylthio-, C1-C4-alkyl- or C1-C4-halogenoalkyl-substituted phenyl, phenoxy or phenylthio,
R6 and R7 independently of one another represent in each case optionally halogen-substituted C1-C10-alkyl, C1-C10-alkoxy, C3-C8-alkenyl or C1-C8-alkoxy-C1-C8-alkyl, represent optionally halogen-, C1-C6-halogenoalkyl-, C1-C6-alkyl- or C1-C6-alkoxy-substituted phenyl, represent optionally halogen-, C1-C6-alkyl-, C1-C6-halogenoalkyl- or C1-C6-alkoxy-substituted benzyl or together represent a 5- or 6-membered ring which is optionally interrupted by oxygen or sulphur and which may optionally be substituted by C1-C6-alkyl,
and
pyrethroids, preferably
1. acrinathrin
known from EP-A-048 186
and/or
2. alpha-cypermethrin
known from EP-A-067 461
and/or
3. betacyfluthrin
known from EP-A-206 149
and/or
4. cyhalothrin
known from DE-A-2 802 962
and/or
5. cypermethrin
known from DE-A-2 326 077
and/or
6. deltamethrin
known from DE-A-2 326 077
and/or
7. esfenvalerate
known from DE-A-2 737 297
and/or
8. ethofenprox
known from DE-A-3 117 510
and/or
9. fenpropathrin
known from DE-A-2 231 312
and/or
10. fenvalerate
known from DE-A-2 335 347
and/or
11. flucythrinate
known from DE-A-2 757 066
and/or
12. lambda-cyhalothrin
known from EP-A-106 469
and/or
13. permethrin
known from DE-A-2 326 077
and/or
14. taufluvalinate
known from EP-A-038 617
and/or
15. tralomethrin
known from DE-A-2 742 546
and/or
16. zeta-cypermethrin
known from EP-A-026 542
and/or
17. cyfluthrin
known from DE-A-27 09 264
and/or
18. bifenthrin
known from EP-A-049 977
and/or
19. cycloprothrin
known from DE-A-2653189
and/or
20. eflusilanate
known from DE-A-36 04 781
and/or
21. fubfenprox
known from DE-A-37 08 231
and/or
22. pyrethrin
R=xe2x80x94CH3 or xe2x80x94CO2CH3
R1=xe2x80x94CHxe2x95x90CH2 or xe2x80x94CH3 or xe2x80x94CH2CH3
known from The Pesticide manual, 1997, 11th edition, p.1056
and/or
23. resmethrin
known from GB-A-1 168 797
have very good insecticidal and acaricidal properties.
Surprisingly, the insecticidal and acaricidal action of the active compound combinations according to the invention considerably exceeds the total of the actions of the individual active compounds. A true synergistic effect which could not have been predicted exists, not just a complementation of action.
The active compound combinations according to the invention comprise, in addition to at least one active compound of the formula (I), at least one active compound of compounds 1 to 23.
Preference is given to active compound combinations comprising compounds of the formula (I)
in which
X represents C1-C4-alkyl, halogen, C1-C4-alkoxy or C1-C2-halogenoalkyl,
Y represents hydrogen, C1-C4-alkyl, halogen, C1-C4-alkoxy or C1-C2-halogenoalkyl,
Z represents C1-C4-alkyl, halogen or C1-C4-alkoxy,
n represents 0 or 1,
A and B together with the carbon atom to which they are attached form a saturated, optionally C1-C4-alkyl- or C1-C4-alkoxy-substituted 5- or 6-membered ring,
G represents hydrogen (a) or represents the groups
in which
R1 represents in each case optionally halogen-substituted C1-C16-alkyl, C2-C16-alkenyl, C1-C6-alkoxy-C2-C6-alkyl or cycloalkyl having 3-7 ring atoms which may be interrupted by 1 or 2 oxygen and/or sulphur atoms,
represents optionally halogen-, nitro-, C1-C4-alkyl-, C1-C4-alkoxy-, C1-C3-halogenoalkyl- or C1-C3-halogenoalkoxy-substituted phenyl,
R2 represents in each case optionally halogen-substituted C1-C16-alkyl, C2-C16-alkenyl or C1-C6-alkoxy-C2-C6-alkyl,
represents in each case optionally halogen-, nitro-, C1-C4-alkyl-, C1-C4-alkoxy- or C1-C4-halogenoalkyl-substituted phenyl or benzyl,
and at least one active compound of compounds 1 to 23.
Particular preference is given to active compound combinations comprising the dihydrofuranone derivative of the formula (I-b-1)
and at least one active compound of compounds 1 to 23.
In addition, the active compound combinations may also comprise other fungicidally, acaricidally or insecticidally active components which may be admixed.
If the active compounds are present in the active compound combinations according to the invention in certain weight ratios, the synergistic effect is particularly pronounced. However, the weight ratios of the active compounds in the active compound combinations may be varied within a relatively wide range. In general, the combinations according to the invention comprise active compounds of the formula (I) and the co-components in the preferred and particularly preferred mixing ratios indicated in the table below:
the mixing ratios are based on weight ratios. The ratio is to be understood as meaning active compound of the formula (I): co-component
The active compound combinations according to the invention are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids found in agriculture, in animal health, in forests, in the protection of stored products and materials and in the hygiene sector. They are active against normally sensitive and resistant species, and against all or individual developmental stages. The abovementioned pests include:
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus carpophagus, Scutigera spp.
From the order of the Symphyla, for example, Scutigerella immaculate.
From the order of the Thysanura, for example, Lepisma saccharina.
From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
From the order of the Blattaria, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Reticulitermes spp.
From the order of the Phthiraptera, for example, Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.
From the order of the Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.
From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp.
From the order of the Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spp.
From the class of the Arachnida, for example, Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.
The plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.
The active compound combinations can be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric materials.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents and/or solid carriers, optionally with the use of surfactants, that is, emulsifiers and/or dispersants, and/or foam formers.
If the extender used is water, it is also possible, for example, to use organic solvents as cosolvents. The following are essentially suitable as liquid solvents: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, or else water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic materials such as highly-disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants such alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
The active compound combinations according to the invention can be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms.
Mixtures with other known active compounds such as herbicides or with fertilizers and growth regulators are also possible.
When used as insecticides, the active compound combinations according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergists. Synergists are compounds which increase the action of the active compounds, without it being necessary for the synergist added to be active itself.
The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate for the use forms.
When used against hygiene pests and stored-product pests, the active compound combinations are distinguished by an excellent residual action on wood and clay as well as good stability to alkali on limed substrates.
The active compound combinations according to the invention are not only active against plant pests, hygiene pests and stored-product pests, but also, in the veterinary medicine sector, against animal parasites (ectoparasites) such as hard ticks, soft ticks, mange mites, harvest mites, flies (stinging and licking), parasitizing fly larvae, lice, hair lice, bird lice and fleas. These parasites include:
From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
From the order of the Mallophagida and the suborders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
From the order Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.
From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.
From the subclass of the Acaria (Acarida) and the order of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Stemostoma spp., Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
The active compound combinations according to the invention are also suitable for controlling arthropods which attack agricultural livestock such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, honey-bees, other domestic animals such as, for example, dogs, cats, caged birds, aquarium fish and so-called experimental animals such as, for example, hamsters, guinea pigs, rats and mice. By controlling these arthropods, cases of death and reductions in productivity (for meat, milk, wool, hides, eggs, honey and the like) should be diminished, so that more economical and simpler animal husbandry is possible by the use of the active compound combinations according to the invention.
The active compound combinations according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration such as, for example, by injections (intramuscularly, subcutaneously, intravenously, intraperitoneally and the like), implants, by nasal administration, by dermal administration in the form of, for example, immersing or dipping, spraying, pouring-on, spotting-on, washing, dusting, and with the aid of active-compound-comprising moulded articles such as collars, ear tags, tail tags, limb bands, halters, marking devices and the like.
When used for cattle, poultry, domestic animals and the like, the active compound combinations can be applied as formulations (for example powders, emulsions, flowables) comprising the active compounds in an amount of 1 to 80% by weight, either directly or after 100- to 10,000-fold dilution, or they may be used as a chemical dip.
Moreover, it has been found that the active compound combinations according to the invention show a potent insecticidal action against insects which destroy industrial materials.
The following insects may be mentioned by way of example and with preference, but not by way of limitation:
Beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus.
Dermapterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.
Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
Bristle-tails such as Lepisma saccharina.
Industrial materials in the present context are understood as meaning non-living materials such as, preferably, polymers, adhesives, glues, paper and board, leather, wood, timber products and paints.
The material which is to be protected from insect attack is very especially preferably wood and timber products.
Wood and timber products which can be protected by the composition according to the invention, or mixtures comprising it, are to be understood as meaning, for example: Construction timber, wooden beams, railway sleepers, bridge components, jetties, vehicles made of wood, boxes, pallets, containers, telephone poles, wood lagging, windows and doors made of wood, plywood, chipboard, joinery, or timber products which quite generally are used in house construction or building joinery.
The active compound combinations can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
The abovementioned formulations can be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or fixative, water repellant, if desired desiccants and UV stabilizers, and if desired colorants and pigments and other processing auxiliaries.
The insecticidal compositions or concentrates used for protecting wood and timber products comprise the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
The amount of composition or concentrate employed depends on the species and the abundance of the insects and on the medium. The optimal quantity to be employed can be determined in each case by test series upon application. In general, however, it will suffice to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
A suitable solvent and/or diluent is an organochemical solvent or solvent mixture and/or an oily or oil-type organochemical solvent or solvent mixture of low volatility and/or a polar organochemical solvent or solvent mixture and/or water and, if appropriate, an emulsifier and/or wetter.
Organochemical solvents which are preferably employed are oily or oil-type solvents with an evaporation number of above 35 and a flash point of above 30xc2x0 C., preferably above 45xc2x0 C. Such oily and oil-type solvents which are insoluble in water and of low volatility and which are used are suitable mineral oils or their aromatic fractions or mineral-oil-containing solvent mixtures, preferably white spirit, petroleum and/or alkylbenzene.
Mineral oils with a boiling range of 170 to 220xc2x0 C., white spirit with a boiling range of 170 to 220xc2x0 C., spindle oil with a boiling range of 250 to 350xc2x0 C., petroleum and aromatics with a boiling range of 160 to 280xc2x0 C., oil of terpentine, and the like are advantageously used.
In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of 180 to 210xc2x0 C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220xc2x0 C. and/or spindle oil and/or monochloronaphthalene, preferably xcex1-monochloronaphthalene are used.
The organic oily or oil-type solvents of low volatility and with an evaporation number of above 35 and a flash point of above 30xc2x0 C., preferably above 45xc2x0 C., can be replaced in part by organochemical solvents of high or medium volatility, with the proviso that the solvent mixture also has an evaporation number of above 35 and a flash point of above 30xc2x0 C., preferably above 45xc2x0 C., and that the mixture is soluble or emulsifiable in this solvent mixture.
In a preferred embodiment, some of the organochemical solvent or solvent mixture is replaced by an aliphatic polar organochemical solvent or solvent mixture. Aliphatic organochemical solvents which contain hydroxyl and/or ester and/or ether groups are preferably used, such as, for example, glycol ethers, esters or the like.
Organochemical binders used for the purposes of the present invention are the synthetic resins and/or binding drying oils which are known per se and which can be diluted in water and/or dissolved or dispersed or emulsified in the organochemical solvents employed, in particular binders composed of, or comprising, an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenol resin, hydrocarbon resin such as indene/coumarone resin, silicone resin, drying vegetable and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.
The synthetic resin employed as binder can be employed in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances may also be used as binders, in amounts of up to 10% by weight. In addition, colorants, pigments, water repellants, odour-masking agents, and inhibitors or anticorrosive agents and the like, all of which are known per se, can be employed.
In accordance with the invention, the composition or the concentrate preferably comprises, as organochemical binders, at least one alkyd resin or modified alkyd resin and/or a drying vegetable oil. Alkyd resins which are preferably used in accordance with the invention are those with an oil content of over 45% by weight, preferably 50 to 68% by weight.
Some or all of the abovementioned binder can be replaced by a fixative (mixture) or plasticizer (mixture). These additives are intended to prevent volatilization of the active compounds, and also crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of binder employed).
The plasticizers are from the chemical classes of the phthalic esters, such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate, phosphoric esters such as tributyl phosphate, adipic esters such as di-(2-ethylhexyl)-adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ethers or higher-molecular-weight glycol ethers, glycerol esters and p-toluenesulphonic esters.
Fixatives are based chemically on polyvinyl alkyl ethers such as, for example, polyvinyl methyl ether, or ketones such as benzophenone and ethylenebenzophenone.
Other suitable solvents or diluents are, in particular, water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersants.
Particularly effective timber protection is achieved by industrial-scale impregnating processes, for example the vacuum, double-vacuum or pressure processes.
The active compound combinations according to the invention can at the same time be employed for protecting objects which come into contact with saltwater or brackish water, such as hulls, screens, nets, buildings, moorings and signalling systems, against fouling. Fouling by sessile Oligochaeta, such as Serpulidae, and by shells and species from the Ledamorpha group (goose barnacles), such as various Lepas and Scalpellum species, or by species from the Balanomorpha group (acorn barnacles), such as Balanus or Pollicipes species, increases the frictional drag of ships and, as a consequence, leads to a marked increase in operation costs owing to higher energy consumption and additionally frequent residence in the dry dock.
Apart from fouling by algae, for example Ectocarpus sp. and Ceramium sp., fouling by sessile Entomostraka groups, which come under the generic term Cirripedia (cirriped crustaceans), is of particular importance.
Surprisingly, it has now been found that the active compound combinations according to the invention have an outstanding antifouling action.
Using the active compound combinations according to the invention, allows the use of heavy metals such as, for example, in bis(trialkyltin) sulphides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride, tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenum disulphide, antimony oxide, polymeric butyl titanate, phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride, manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zinc oxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, copper naphthenate and tributyltin halides to be dispensed with, or the concentration of these compounds substantially reduced.
If appropriate, the ready-to-use antifouling paints can additionally comprise other active compounds, preferably algicides, fungicides, herbicides, molluscicides, or other antifouling active compounds.
Preferably suitable components in combinations with the antifouling compositions according to the invention are:
algicides such as 2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophen, diuron, endothal, fentine acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
fungicides such as benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide, dichlofluanid, fluor-folpet, 3-iodo-2-propinyl butylcarbamate, tolylfluanid and azoles such as azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and tebuconazole;
molluscicides such as fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and trimethacarb;
or conventional antifouling active compounds such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl sulfone, 2-(N,N-di-methylthiocarbamoylthio)-5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6-trichlorophenylmaleiimide.
The antifouling compositions used comprise the active compound combinations according to the invention in a concentration of 0.001 to 50% by weight, in particular 0.01 to 20% by weight.
Moreover, the antifouling compositions according to the invention comprise the customary components such as, for example, those described in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
Besides the algicidal, fungicidal, molluscicidal active compounds and insecticidal active compounds according to the invention, antifouling paints comprise, in particular, binders.
Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, in particular in an aqueous system, vinyl chloride/vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene/styrene/acrylonitrile rubbers, drying oils such as linseed oil, resin esters or modified hardened resins in combination with tar or bitumens, asphalt and epoxy compounds, small amounts of chlorine rubber, chlorinated polypropylene and vinyl resins.
If appropriate, paints also comprise inorganic pigments, organic pigments or colorants which are preferably insoluble in salt water. Paints may furthermore comprise materials such as colophonium to allow controlled release of the active compounds. Furthermore, the paints may comprise plasticizers, modifiers which affect the rheological properties and other conventional constituents. The compounds according to the invention or the abovementioned mixtures may also be incorporated into self-polishing antifouling systems.
The active compound combinations are also suitable for controlling animal pests, in particular insects, arachnids and mites, which are found in enclosed spaces such as, for example, dwellings, factory halls, offices, vehicle cabins and the like. They can be employed in domestic insecticide products for controlling these pests. They are active against sensitive and resistant species and against all developmental stages. These pests include:
From the order of the Scorpionidea, for example, Buthus occitanus.
From the order of the Acarina, for example, Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
From the order of the Araneae, for example, Aviculariidae, Araneidae.
From the order of the Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
From the order of the Isopoda, for example, Oniscus asellus, Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp.
From the order of the Chilopoda, for example, Geophilus spp.
From the order of the Zygentoma, for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
From the order of the Blattaria, for example, Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
From the order of the Saltatoria, for example, Acheta domesticus.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Kalotermes spp., Reticulitermes spp.
From the order of the Psocoptera, for example, Lepinatus spp., Liposcelis spp.
From the order of the Coleptera, for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
From the order of the Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.
From the order of the Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
From the order of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
From the order of the Anoplura, for example, Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis.
From the order of the Heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans. They are used as aerosols, pressure-free spray products, for example pump and atomizer sprays, automatic fogging systems, foggers, foams, gels, evaporator products with evaporator tablets made of cellulose or polymer, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free, or passive, evaporation systems, moth papers, moth bags and moth gels, as granules or dusts, in baits for spreading or in bait stations.
All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (inclusive of naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and recombinant methods or by combinations of these methods, inclusive of the transgenic plants and inclusive of the plant varieties protectable or not protectable by plant breeders"" rights, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offsets and seeds.
Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on the surroundings, environment or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on and, in the case of propagation material, in particular in the case of seed, also by applying one or more coats.
The good insecticidal and acaricidal action of the active compound combinations according to the invention can be seen from the examples which follow. While the individual active compounds show weaknesses in their action, the combinations show an action which exceeds a simple sum of actions.
A synergistic effect in insecticides and acaricides is always present when the action of the active compound combinations exceeds the total of the actions of the active compounds when applied individually.
The expected action for a given combination of two active compounds can be calculated as follows, using the formula of S. R. Colby, Weeds 15(1967), 20-22:
If
X is the efficacy, expressed as % of the untreated control, when employing active compound A at an application rate of m g/ha or in a concentration of m ppm,
Y is the efficacy, expressed as % of the untreated control, when employing active compound B at an application rate of n g/ha or in a concentration of n ppm and
E is the efficacy, expressed as % of the untreated control, when employing active compounds A and B at application rates of m and n g/ha or in a concentration of m and n ppm,
then   E  =      X    +    Y    -                  X        ·        Y            100
If the actual insecticidal kill rate exceeds the calculated value, the action of the combination is superadditive, i.e. a synergistic effect is present. In this case, the actually observed insecticidal kill rate must exceed the value calculated using the above formula for the expected insecticidal kill rate (E).
After the desired period of time, the kill in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.

Active substance combinations comprising insecticidal and acaricidal properties


A sensor retainer for a bicycle sprocket assembly includes an annular member for mounting and rotating coaxially with the bicycle sprocket assembly and a sensor element fixed to the annular member. Alternatively, the sensor retainer may include a fixing member for mounting a derailleur or other transmission to a bicycle frame and a sensor element mounted to the fixing member.

The present invention is directed to electrical shift control devices for bicycle transmissions and, more particularly, to a motion sensor for use with a bicycle sprocket assembly.
Motion sensors are commonly used with bicycles to sense rotation of the wheel or pedal crank so that bicycle speed and cadence may be computed by a bicycle computer and displayed to the rider. Such information also may be used to control an automatic or semiautomatic bicycle transmission, wherein the bicycle speed or cadence may be used to determine when to change gear ratios. The typical motion sensor usually comprises a magnet attached to the wheel or crank arm and a magnetic sensor attached to the bicycle frame. When the magnet passes in close proximity to the magnetic sensor, the sensor provides a pulse to the bicycle computer. The speed or cadence then may be computed based on the elapsed time between successive pulses.
A disadvantage of traditional motion sensors is that they increase the number of parts at various locations on the bicycle, thus giving the bicycle a cluttered appearance. Furthermore, the appearance of a magnet rotating with the spokes can be disconcerting. Also, as the number of electronically controlled components increases, the amount of wiring needed to connect the various components together also increases. For example, if the bicycle uses an electronically controlled transmission, then wires must be routed for the wheel magnetic sensor, the crank magnetic sensor, the front transmission and the rear transmission. The aesthetic appearance of the bicycle is greatly diminished by such excessive wiring.
The present invention is directed to a motion sensor for use with a bicycle sprocket assembly wherein a magnet or first sensor element is mounted for rotation with the sprocket assembly. Another feature of the present invention is a magnetic sensor or second sensor element being mounted in close proximity to the bicycle transmission. Associating the first sensor element with the sprocket assembly eliminates the requirement of mounting the first sensor element on the spokes, and mounting the second sensor element in close proximity to the bicycle transmission allows the wiring for the second sensor element, if any, to be combined with any wiring or cables already routed to the transmission. The present invention thus combines various structures and functions in proximity to each other and results in a less cluttered appearance for the bicycle.
In one embodiment of the present invention, a sensor retainer for a bicycle sprocket assembly includes an annular member for mounting and rotating coaxially with the bicycle sprocket assembly and a sensor element fixed to the annular member. Alternatively, the sensor retainer may include a fixing member for mounting a derailleur or other transmission to a bicycle frame and a sensor element mounted to the fixing member.
In a more specific embodiment, a sensor assembly for a bicycle includes a plurality of sprockets mounted together for rotation around a common axis; a first sensor element coupled for rotation with the plurality of sprockets; and a second sensor element for attachment in close proximity to the plurality of sprockets so that the first sensor element rotates relative to the second sensor element. If desired, the first sensor element may include a signal generating element such as a magnet, and the second sensor element may include a signal receiving element such as a magnetic sensor. The second sensor element may include a first sensor unit for communicating with the first sensor element and a second sensor unit for communicating with the first sensor element, wherein the first sensor unit is offset from the second sensor unit in a circumferential direction. Such a structure allows the direction of rotation as well as the speed of rotation of the plurality of sprockets to be determined.
In another embodiment of the present invention, the plurality of sprockets may include a first sprocket and a second sprocket, wherein the first sprocket includes a shift facilitating structure for facilitating shifting of a chain from the second sprocket to the first sprocket. In this embodiment the first sensor element may be located at a specified rotational position relative to the shift facilitating structure so that the position of the shift facilitating structure may be determined. This feature has special usefulness when the sensor assembly is used in conjunction with an electronically controlled derailleur because then the derailleur may be commanded to shift the chain from the second sprocket to the first sprocket when the shift facilitating structure is in the optimum rotational position.

Motion sensor for use with a bicycle sprocket assembly


A polypropylene fibre including a polypropylene blend comprising up to 15% by weight of sPP at least 10% by weight of a first isotactic polypropylene produced by a metallocene catalyst, and optionally a second isotactic polypropylene produced by a Ziegler-Natta catalyst.

The present invention relates to polypropylene fibres and to fabrics produced from polypropylene fibres.
Polypropylene is well known for the manufacture of fibres, particularly for manufacturing non woven fabrics.
EP-A-0789096 discloses such polypropylene fibres which are made of a blend of syndiotactic polypropylene (sPP) and isotactic polypropylene (iPP). That specification discloses that by blending from 0.3 to 3% by weight of sPP, based on the total polypropylene, to form a blend of iPP-sPP, the fibres have increased natural bulk and smoothness, and non-woven fabrics produced from the fibres have an improved softness. Moreover, that specification discloses that such a blend lowers the thermal bonding temperature of the fibres. Thermal bonding is employed to produce the non-woven fabrics from the polypropylene fibres.
The specification discloses that the isotactic polypropylene comprises a homopolymer formed by the polymerisation of propylene by Ziegler-Natta catalysis. The isotactic polypropylene typically has a weight average molecular weight Mw of from 100,000 to 4,000,000 and a number average molecular weight Mn of from 40,000 to 100,000, with a melting point of from about 159 to 169xc2x0 C. However, the polypropylene fibres produced in accordance with this specification suffer from the technical problem that the isotactic polypropylene, being made using a Ziegler-Natta catalyst, does not have particularly high mechanical properties, particularly tenacity.
WO-A-96/23095 discloses a method for providing a non-woven fabric with a wide bonding window in which the non-woven fabric is formed from fibres of a thermoplastic polymer blend including from 0.5 to 25 wt % of syndiotactic polypropylene. The syndiotactic polypropylene may be blended with a variety of different polymers, including isotactic polypropylene. The specification includes a number of examples in which various mixtures of syndiotactic polypropylene with isotactic polypropylene were produced. The isotactic polypropylene comprised commercially available isotactic polypropylene, which is produced using a Ziegler-Natta catalyst. It is disclosed in the specification that the use of syndiotactic polypropylene widens the window of temperature over which thermal bonding can occur, and lowers the acceptable bonding temperature.
WO-A-96/23095 also discloses the production of fibres from blends including syndiotactic polypropylene which are either bi-component fibres or bi-constituent fibres. Bi-component fibres are fibres which have been produced from at least two polymers extruded from separate extruders and spun together to form one fibre. Bi-constituent fibres are produced from at least two polymers extruded from the same extruder as a blend. Both bi-component and bi-constituent fibres are disclosed as being used to improve the thermal bonding of Ziegler-Natta polypropylene in non-woven fabrics. In particular, a polymer with a lower melting point compared to the Ziegler-Natta isotactic polypropylene, for example polyethylene, random copolymers or terpolymers, is used as the outer part of the bi-component fibre or blended in the Ziegler-Natta polypropylene to form the bi-constituent fibre.
EP-A-0634505 discloses improved propylene polymer yarn and articles made therefrom in which for providing yarn capable of increased shrinkage syndiotactic polypropylene is blended with isotactic polypropylene with there being from 5 to 50 parts per weight of syndiotactic polypropylene. It is disclosed that the yarn has increased resiliency and shrinkage, particularly useful in pile fabric and carpeting. It is disclosed that the polypropylene blends display a lowering of the heat softening temperature and a broadening of the thermal response curve as measured by differential scanning calorimetry as a consequence of the presence of syndiotactic polypropylene.
U.S. Pat. No. 5,269,807 discloses a suture fabricated from syndiotactic polypropylene exhibiting a greater flexibility than a comparable suture manufactured from isotactic polypropylene. The syndiotactic polypropylene may be blended with, inter alia, isotactic polypropylene.
EP-A-0451743 discloses a method for moulding syndiotactic polypropylene in which the syndiotactic polypropylene may be blended with a small amount of a polypropylene having a substantially isotactic structure. It is disclosed that fibres may be formed from the polypropylene. It is also disclosed that the isotactic polypropylene is manufactured by the use of a catalyst comprising titanium trichloride and an organoaluminium compound, or titanium trichloride or titanium tetrachloride supported on magnesium halide and an organoaluminium compound, i.e. a Ziegler-Natta catalyst.
EP-A-0414047 discloses polypropylene fibres formed of blends of syndiotactic and isotactic polypropylene. The blend includes at least 50 parts by weight of the syndiotactic polypropylene and at most 50 parts by weight of the isotactic polypropylene. It is disclosed that the extrudability of the fibres is improved and the fibre stretching conditions are broadened.
EP-A-0894875 discloses bicomponent fibres of isotactic and syndiotactic polypropylene in which an isotactic polypropylene component and a syndiotactic polypropylene component are each fused to the other along the fibre axis. This specification does not address the problem of the manufacture of non-woven fabrics by thermal bonding.
EP-A-0832924 relates to a polyolefin moulding composition for producing high strength non-woven fabric.
WO-A-97/10300 discloses polypropylene blend compositions comprising propylene copolymer having a broad molecular weight distribution. The first and second propylene polymers of the blend are preferably isotactic.
EP-A-0870779 discloses a metallocene catalyst system for producing a polypropylene blend of iso- and syndiotactic polypropylene.
EP-A-0284707 discloses a hafnium metallocene catalyst for the polymerisation of olefins, in particular to make isotactic polypropylene.
EP-A-0427696 discloses a process and catalyst for producing syndiotactic polymers, in particular syndiotactic polypropylene using metallocene catalysts.
It is further known to produce syndiotactic polypropylene using metallocene catalysts as has been disclosed for example in U.S. Pat. No. 4,794,096.
Recently, metallocene catalysts have also been employed to produce isotactic polypropylene. Isotactic polypropylene which has been produced using a metallocene catalyst is identified hereinafter as miPP. Fibres made of miPP exhibit much higher mechanical properties, mainly tenacity, than typical Ziegler-Natta polypropylene based fibres, hereinafter referred to as znPP fibres. However, this gain in tenacity is only partly transferred to non-woven fabrics which have been produced from the miPP fibres by thermal bonding. Indeed, fibres produced using miPP have a very narrow thermal bonding window, the window defining a range of thermal bonding temperatures through which, after thermal bonding of the fibres, the non-woven fabric exhibits the best mechanical properties. As a result, only a small number of the miPP fibres contribute to the mechanical properties of the non-woven fabric. Also, the quality of the thermal bond between adjacent miPP fibres is poor. Thus known miPP fibres have been found to be more difficult to thermally bond than znPP fibres, despite a lower melting point.
It is an aim of the present invention to broaden the thermal bonding window of miPP fibres. It is a further aim of the invention to provide non-woven fabrics of miPP fibres exhibiting improved mechanical properties, in particular tenacity.
It is known that polypropylene fibres, and non-woven fabrics made of polypropylene fibres, tend to feel rough to the touch. It is also an aim of the present invention to improve the softness of miPP polypropylene fibres.
The present invention provides a polypropylene fibre including a polypropylene blend comprising up to 15% by weight of sPP, at least 10% by weight of a first isotactic polypropylene produced by a metallocene catalyst, and optionally a second isotactic polypropylene produced by a Ziegler-Natta catalyst.
Preferably, the sPP concentration in the sPP/miPP blend is from 3 to 15 wt %. The fibre may be a two component sPP/miPP blend, including at least 85 wt % miPP. When present, the znPP may be a homopolymer, copolymer or terpolymer.
Preferably, the miPP is a homopolymer, copolymer, being either a random or block copolymer, or terpolymer of isotactic polypropylene produced by a metallocene catalyst.
Preferably, the first polypropylene has a dispersion index (D) of from 2 to 3.5. Preferably, the first polypropylene has a melting temperature in the range of from 140 to 155xc2x0 C. for homopolymer and a melting temperature of from 80 to 150xc2x0 C. for a copolymer or terpolymer.
The miPP preferably has a melt flow index (MFI) of from 1 to 2500 g/10 mins. In this specification the MFI values are those determined using the procedure of ISO 1133 using a load of 2.16 kg at a temperature of 230xc2x0 C.
More preferably, the first polypropylene homopolymer has an Mn of from 50,000 to 100,000 kDa and the MFI may range from 15 to 90 g/10 min for spunlaid or staple fibres. The MFI may range from 350 to 2500 g/10 min for the first polypropylene being a copolymer or a terpolymer having a higher Mn than for the homopolymer for making melt blown fibres.
The sPP is preferably a homopolymer or a random copolymer with a comonomer content of from 0.1 to 1.5 wt %. The sPP may alternatively be a block copolymer having a higher comonomer content, or a terpolymer. If the comonomer content is above 1.5 wt %, the sPP tends to become sticky, thus resulting in problems when spinning the fibres or thermally bonding the fibres. The comonomer content is selected so as to decrease the melting point of the sPP iPP blend below 130xc2x0 C. A lower melting point can also be obtained by using particular catalysts and/or process conditions during polymerisation of the sPP. Preferably, the sPP has a melting temperature of up to about 130xc2x0 C. The sPP typically has two melting peaks, one being around 112xc2x0 C. and the other being around 128xc2x0 C. The sPP typically has an MFI of from 0.1 to 1000 g/10 min, more typically from 1 to 60g/10 min. The sPP may have a monomodal or multimodal molecular weight distribution, and most preferably is a bimodal polymer in order to improve the processability of the sPP. The properties of a typical bimodal sPP for use with the invention are specified in Table 1.
The present invention further provides a polypropylene fibre including a polypropylene blend comprising up to 15% by weight of sPP, at, least 10% by weight of a first isotactic polypropylene homopolymer, copolymer or terpolymer having a melting temperature of from 80xc2x0 C. to 155xc2x0 C., and optionally a second isotactic polypropylene homopolymer or copolymer having a melting temperature of from 159xc2x0 C. to 169xc2x0 C.
Preferably, the first isotactic polypropylene has a dispersion index (D) of from 2 to 3.5.
Preferably, the second isotactic polypropylene has a dispersion index (D) of from 3 to 9.
The present invention further provides a fabric produced from the polypropylene fibre of the invention.
The present invention yet further provides a product including that fabric, the product being selected from among others a filter, personal wipe, diaper, feminine hygiene product, incontinence product, wound dressing, bandage, surgical gown, surgical drape and protective cover.
The present invention is predicated on the discovery by the present inventor that when blended with miPP, even in small concentrations, sPP is rejected to the surface of the polypropylene fibres during the spinning process. Accordingly, when blending miPP, which has a typical melting range of from around 140C to around 155xc2x0 C., with sPP, which typically has a melting range of from about 80xc2x0 C. to about 130xc2x0 C., even though only a small concentration of sPP is incorporated into the miPP, as a result of the rejection of the sPP to the surface of the fibres, the range of temperature through which the fibres can be thermally bonded, is broadened and shifted to lower temperatures. As a consequence, at any given thermal bonding temperature, more fibres are thermally bonded and bonding strength improves, thereby improving the mechanical properties of the non-woven fabric produced thereby.
Since the sPP has a melting peak about 15xc2x0 C. lower than that of the miPP and is rejected to the surface of the fibres during the spinning process, as a consequence when thermally bonding the fibres at a lower temperature than the optimal thermal bonding temperature for pure miPP fibres, the sPP contributes to improving the strength of the thermally bonded points, hence broadening the thermal bonding window.
The present inventor has found that when used in an amount of only about 2 to 3 wt % sPP in the sPP/miPP blend, the thermal bondability is increased, as a result of the sPP being rejected to the surface of the fibres during the spinning process. The known Ziegler-Natta isotactic polypropylene fibres, such as those disclosed in the patent specifications identified hereinabove, typically have a melting temperature of around 159-169xc2x0 C., for example 162xc2x0 C. The difference in temperature between the known Ziegler-Natta isotactic polypropylene fibres and the sPP incorporated therein in the patent specifications referred to hereinabove has provided improved properties. However, for miPP utilised in accordance with the present invention, the typical melting point is around 140xc2x0 C. to 155xc2x0 C., which is typically around 15xc2x0 C. to 20xc2x0 C. higher than that for the sPP, but also significantly lower than that of the Ziegler-Natta isotactic polypropylene.
Comonomer addition into the sPP allows the melting point to decrease. As a consequence, comonomer concentration may be adjusted to reach the desired melting temperature, whereby the miPP and the sPP have a melting peak difference of about 15xc2x0 C. to 20xc2x0 C. The combination of the relatively low melting peak difference between on the one hand the miPP and on the other hand the sPP and also the provision of the sPP on the surface of the fibres following the spinning process provides significant advantages when the fibres are employed to make thermally bonded non-woven fabrics. An industrial thermal bonding process for producing a non-woven fabric employs the passage at high speed of a layer of fibres to be thermally bonded through a pair of heated rollers. This process thus requires rapid and uniform melting of the surfaces of adjacent fibres in order for a strong and reliable thermal bond to be achieved. The addition of sPP to the miPP lowers the thermal bonding temperature of the fibres and broadens the thermal bonding temperature range or xe2x80x9cwindowxe2x80x9d for the fibres, thus increasing the ease of thermal bonding the fibres together. Since the sPP tends to be at the surface of the fibres and since the miPP has a melting point range which is only slightly higher than that of the sPP so that there is a melting temperature overlap between the sPP and the miPP in the thermal bonding temperature window, when the fibres are thermally bonded, which can be achieved at lower-temperatures than for miPP alone, the increased breadth of the thermal bonding window can provide that not only is the sPP on the surface of the fibres melted, but also some of the miPP tends to be melted, to form bonds between adjacent fibres. Thus the incorporation of sPP into miPP enables the maximum strength of the non-woven fabric to be greatly increased as a result of this increased thermal bond formation between adjacent fibres.
In contrast, znPP has a significantly higher melting point range than that for sPP so that when the known znPP/sPP fibres are thermally bonded, the thermal bonding, and thus the tenacity are lower than for the miPP/sPP blends of the invention because the znPP does not contribute to the formation of thermal bonds.
The miPP employed in accordance with the invention has a narrow molecular weight distribution, typically having a dispersion index D of from 2 to 3.5, more preferably from 2 to 3. The dispersion index D is the ratio Mw/Mn, where Mw is the weight number average molecular weight and Mn is the number average molecular weight of the polymer. The miPP typically has a peak in the molecular weight distribution of 60,000 to 120,000 kDa. The miPP has a melting temperature in the range of from 140xc2x0 C. to 155xc2x0 C. The properties of two typical miPP resins for use in the invention are specified in Table 1.
In contrast, the sPP has a slightly broader molecular weight distribution than for the miPP, wherein typically D may be around 4 and has a peak of the molecular weight distribution at around 20,000 to 40,000 kDa. The sPP has a melting temperature of up to about 130xc2x0 C. In view of the separation between the peaks and the substantial non-overlap of the molecular weight distributions of the sPP and the miPP, it is surprising that those two components can in fact readily be blended together. The sPP tends to be provided at the surface of the miPP fibres. As stated above, this provides an advantage in thermal bonding. Since there is an overlap in the melting point range in the miPP and the sPP, there is an increase in thermal bonding between the fibres, and this increase is manifested in an increase tenacity for non-woven fabrics produced in accordance with the invention, with tenacity increasing with an increase in the amount of sPP. This is because any increase in sPP tends to be increase the amount of material thermally bonded on the surface of the fibres. However, for sPP amounts greater than about 15 to 20 wt %, the amount varying depending upon other parameters, such as the particular processing conditions for spinning the fibres, the tenacity can tend to decrease.
The addition of sPP to the miPP also has been found by the inventor to improve the softness of the fibres. As a result of this surface rejection phenomenon, the inventor has found that the softness of the fibres may be increased using only small amounts of sPP, for example from 0.3 wt % sPP in the sPP/miPP blend. Since the blending of sPP into miPP permits a lower thermal bonding temperature to be employed than would be employed for pure miPP fibres, and since lower thermal bonding temperatures tend to reduce the roughness to the touch of a non-woven fabric produced from the fibres, introducing sPP in accordance with the invention into miPP improves the softness of the non-woven fabric.
Furthermore, in accordance with the invention when sPP is incorporated into miPP to form blends thereof, and when those blends are used to produce spun fibres, the sPP promotes fibres having improved natural bulk, resulting in improved softness of the non-woven fabric.
In addition, the use of miPP in blends with sPP in accordance with the invention tends to provide fibres which can be more readily spun as compared to known znPP fibres. The substantial absence of such long chains in the molecular weight distribution of the miPP tends to reduce built-in stress during spinning thereby to allow in an increase in the maximum spin speed for the fibres of the sPP/miPP blends in accordance with the invention.
In accordance with the invention, the incorporation of sPP into miPP to form blends thereof provides a broader thermal bonding window, allowing transfer of the properties of the miPP fibres into the properties of the non-woven fabrics produced from the blends. The thermal bonding temperature of fibres produced from such blends is also slightly lower. The fibres and non-woven fabrics produced from the blends have increased softness and the spun fibres have natural bulk as a result of the introduction of sPP into the miPP. The fibres also have improved resiliency compared to known polypropylene znPP fibres as a result of the use of sPP. Furthermore, the use of miPP allows the production of finer fibres, resulting in softer fibres and a more homogeneous distribution of the fibres in the non-woven fabric.
Although it was known prior to the present invention to use a second polymer in fibres, it has not heretofore been proposed to employ sPP in a blend with miPP for the production of fibres. The use of sPP provides optimum thermal characteristics that help improve the thermal bonding of the miPP fibres. Efficient thermal bonding of the fibres is required to transfer the outstanding mechanical properties of miPP fibres into non-woven fabrics. In addition, only a few percent of sPP is enough to observe a significant improvement in the mechanical properties such as thermal bondability and softness of the fibres and non-woven fabrics, whereas with other polymers much larger quantities are required. As a consequence, the spinnability of the fibres produced using sPP/miPP blends in accordance with the invention is not significantly modified as compared to known fibres.
The fibres produced in accordance with the invention may be either bi-component fibres or bi-constituent fibres. For bi-component fibres, miPP and sPP are fed into two different extruders. Thereafter the two extrudates are spun together to form single fibres. For the bi-constituent fibres, blends of sPP/miPP are obtained by: dry blending pellets, flakes or fluff of the two polymers before feeding them into a common extruder; or using pellets or flakes of a blend of sPP and miPP which have been extruded together and then re-extruding the blend from a second extruder.
When the blends of sPP/miPP are used to produce fibres in accordance with the invention, at up to 15 wt % sPP there is no significant effect on the spinning characteristics of the blends. For the production of spunlaid fibres, a typical extrusion temperature would be in the range of from 200xc2x0 C. to 260xc2x0 C., most typically from 230xc2x0 C. to 250xc2x0 C. For the production of staple fibres, a typical extrusion temperature would be in the range of from 230xc2x0 C. to 330xc2x0 C., most typically from 280xc2x0 C. to 300xc2x0 C.
The fibres produced in accordance with the invention may be produced from sPP/miPP blends having other additives to improve the mechanical processing or spinnability of the fibres. The fibres produced in accordance with the invention may be used to produce non-woven fabrics for use in filtration; in personal care products such as wipers, diapers, feminine hygiene products and incontinence products; in medical products such as wound dressings, surgical gowns, bandages and surgical drapes; in protective covers; in outdoor fabrics and in geotextiles. Non-woven fabrics made with the sPP/miPP fibres of the invention can be part of such products, or constitute entirely the products. As well as making non-woven fabrics, the fibres may also be employed to make a knitted fabric or a mat. The non-woven fabrics produced from the fibres in accordance with the invention can be produced by several processes, such as air through blowing, melt blowing, spun bonding or bonded carded processes. The fibres of the invention may also be formed as a non-woven spunlace- product which is formed without thermal bonding by fibres being entangled together to form a fabric by the application of a high pressure-fluid such as air or water.