The present invention relates to a herbicidal composition comprising

The invention lies in the technical field of the crop protection products; in particular, the invention relates to herbicidal compositions comprising certain sulfonylureas and/or their salts and specific surfactants, which compositions are outstandingly suitable for controlling harmful plants in crop plants.
The use of sulfonylureas as active component of crop protection compositions is known (for example EP-A-007 687, EP-A-030 138). Likewise, it is known to combine sulfonylureas such as nicosulfuron (Accent(copyright)) with surfactants (for example Weed Technology 1999, Vol. 13, pages 737-740).
It was an object of the present invention to provide herbicidal compositions having particularly high herbicidal activity.
Surprisingly, it has now been found that this object is achieved by herbicidal compositions which comprise certain sulfonylureas in combination with specific surfactants.
The present invention thus relates to herbicidal compositions comprising
A) one or more sulfonylureas of the formula (I) and/or their salts
in which
R1 is C2-C4-alkoxy or COxe2x80x94Ra, where Ra is OH, C1-C6-alkoxy or NRbRc, where Rb and Rc independently of one another are identical or different and are H or C1-C6-alkyl,
R2 is halogen or (A)nxe2x80x94NRdRe, where n is zero or 1, A is a group CRfRg, where Rf and Rg independently of one another are identical or different and are H or C1-C6-alkyl, Rd is H or C1-C6-alkyl and Re is H, C1-C6-alkyl or an acyl radical, where Rd and Re may also form a heterocyclic ring and where, if R1 is C2-C4-alkoxy, R2 may also be H,
R3 is H or C1-C6-alkyl,
m is zero or 1,
X and Y independently of one another are identical or different and are C1-C6-alkyl, C1-C6-alkoxy or C1-C6-alkylthio, where each of the three radicals mentioned is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, C1-C4-alkoxy and C1-C4-alkylthio, or are C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-alkenyloxy or C3-C6-alkynyloxy, preferably C1-C4-alkyl or C1-C4-alkoxy,
Z is CH or N,and
B) one or more surfactants comprising as structural element at least 10, preferably 10-200, alkylene oxide units.
Surfactant B) preferably contains 10-150 alkylene oxide units, one or more C1-C40-carbon-containing radicals and optionally one or more polar functional groups.
The term alkylene oxide units is preferably to be understood as meaning units of C2-C10-alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or hexylene oxide, where the units within the surfactant may be identical to or different from one another.
Suitable polar functional groups are, for example, anionic groups, such as carboxylate, carbonate, sulfate, sulfonate, phosphate or phosphonate, cationic groups, such as groups having a cationic nitrogen atom, for example a pyridinium group or an xe2x80x94NRy3 group, where Ry are identical or different and are H or unsubstituted or substituted C1-C10-hydrocarbon radicals, such as C1-C10-alkyl, electrically neutral polar groups, such as carbonyl, imine, cyano or sulfonyl, or betainic groups, such as
where m=1, 2, 3, 4 or 5 and Rx are identical or different unsubstituted or substituted C1-C10-hydrocarbon radicals, such as C1-C10-alkyl.
Preferably, the composition according to the invention comprises, as component B), one or more surfactants of the formula (II)
R4xe2x88x92(EO)x(PO)y(EO)zxe2x88x92R5xe2x80x83xe2x80x83(II)
in which
EO is an ethylene oxide unit,
PO is a propylene oxide unit,
x is an integer from 1 to 50,
y is an integer from 0 to 50,
z is an integer from 0 to 50,
where the sum (x+y+z) is xe2x89xa710 and xe2x89xa6150, and
R4 is OH, an unsubstituted or substituted C1-C40-hydrocarbonoxy radical, an O-acyl radical, such as Oxe2x80x94CORI, Oxe2x80x94COxe2x80x94ORI, Oxe2x80x94COxe2x80x94NRIRII, Oxe2x80x94P(O)(RI)[(EO)u(ORII)] or Oxe2x80x94P(O)[(EO)u(ORI)][(EO)v(ORII)], or NRIRII or [NRIRIIRIII]⊕Xxe2x8ax96, where RI, RII and RIII are identical or different and are H or an unsubstituted or substituted C1-C30-hydrocarbon radical which may be attached via a group (EO)w, where w is an integer from 1 to 50, Xxe2x8ax96 being an anion (for example the anion of an organic acid, such as a carboxylic acid anion, for example acetate or lactate, or the anion of an inorganic acid, such as xc2xd sulfate, [Oxe2x80x94SO3xe2x80x94CH3]xe2x8ax96, sulfonate, ⅓ phosphate, phosphonate or halide, such as Clxe2x8ax96 or Brxe2x8ax96), and u and v independently of one another being integers from 0 to 50, and
R5 is H, an unsubstituted or substituted C1-C40-hydrocarbon radical, an acyl radical, such as CORI, COxe2x80x94ORI, COxe2x80x94NRIRII, P(O)(RI)[(EO)u(ORII)] or P(O)[(EO)u(ORI)][(EO)v(ORII)], or NRIRII or [NRIRIIRIII]⊕Xxe2x8ax96, where RI, RII and RIII are identical or different and are H or an unsubstituted or substituted C1-C30-hydrocarbon radical which may be attached via a group (EO)w, where w is an integer from 1 to 50, Xxe2x8ax96 being an anion (for example the anion of an organic acid, such as a carboxylic acid anion, for example acetate or lactate, or the anion of an inorganic acid, such as xc2xd sulfate, [Oxe2x80x94SO3xe2x80x94CH3]xe2x8ax96, sulfonate, ⅓ phosphate, phosphonate or halide, such as Clxe2x8ax96 or Brxe2x8ax96), and u and v independently of one another being integers from 0 to 50.
The abbreviation EO in formula (II) denotes an ethylene oxide unit, likewise when used in the definition of R4 and R5.
Preference is given to surfactants of the formula (II) in which the sum (x+y+z) is xe2x89xa710 and xe2x89xa6150, preferably 11-100, particularly preferably 12-80, and
R4 is OH, an unsubstituted or substituted C1-C30-, preferably C4-C20-, hydrocarbonoxy radical, such as a C8-, C10-, C12-, C13- (for example isotridecyl-), C14-, C16-, C18-, C20-alkoxy radical, -alkenyloxy radical or -alkynyloxy radical, or an unsubstituted or substituted, for example mono- or poly-C1-C20-alkyl-substituted, C6-C14-aryloxy radical, such as p-octylphenoxy, p-nonylphenoxy, 2,4-dibutylphenoxy, 2,4,6-triisobutylphenoxy, 2,4,6-tri-n-butylphenoxy or 2,4,6-tri-sec-butylphenoxy, or R4 is Oxe2x80x94COxe2x80x94RI, Oxe2x80x94COORI, NRIRII or [NRIRIIRIII]⊕Xxe2x8ax96, where RI, RII and RIII are identical or different and are H, an unsubstituted or substituted C8-C30-, preferably C4-C20-, hydrocarbon radical, such as a C8-, C10-, C12-, C3- (for example isotridecyl-), C14-, C16-, C18-, C20-alkyl radical, -alkenyl radical or -alkynyl radical, or an unsubstituted or substituted, for example mono- or poly-C1-C20-alkyl-substituted, C6-C14-aryl radical, such as p-octylphenyl, p-nonylphenyl, 2,4-dibutylphenyl, 2,4,6-triisobutylphenyl, 2,4,6-tri-n-butylphenyl or 2,4,6-tri-sec-butylphenyl, or RI, RII and RIII are identical or different (EO)w-RIV, where RIV is H or an unsubstituted or substituted C1-C20-hydrocarbon radical, such as a C8-, C10-, C12,C13- (for example isotridecyl-), C14-, C16-, C18-, C20-alkyl radical, -alkenyl radical or -alkynyl radical, or an unsubstituted or substituted, for example mono- or poly-C1-C20-alkyl-substituted, C6-C14-aryl radical, such as p-octylphenyl, p-nonylphenyl, 2,4-dibutylphenyl, 2,4,6-triisobutylphenyl, 2,4,6-tri-n-butylphenyl or 2,4,6-tri-sec-butylphenyl, and w is an integer from 1 to 50, Xxe2x8ax96 being an anion, and
R5 is H, an unsubstituted or substituted C1-C30-, preferably C1-C20-, hydrocarbon radical, such as a C1-, C2-, C3-, C4-, C5-, C6-, C8-, C10-, C12-, C13- (for example isotridecyl-), C14-, C16-, C18, C20-alkyl radical, -alkenyl radical or -alkynyl radical, or an unsubstituted or substituted, for example mono- or poly-C1-C20-alkyl-substituted, C6-C14-aryl radical, such as p-octylphenyl, p-nonylphenyl, 2,4-dibutylphenyl, 2,4,6-triisobutylphenyl, 2,4,6-tri-n-butylphenyl or 2,4,6-tri-sec-butylphenyl, or R5 is COxe2x80x94RI, COORI, NRIRII or [NRIRIIRIII]⊕Xxe2x8ax96, where RI, RII and RIII are identical or different and are H, an unsubstituted or substituted C1-C30-, preferably C1-C20-, hydrocarbon radical, such as a C1-, C2-, C3-, C4-, C5-, C6-, C8- C10, C12-, C13- (for example isotridecyl-), C,14-, C16-, C,18-, C20-alkyl radical, -alkenyl radical or -alkynyl radical, or an unsubstituted or substituted, for example mono- or poly-C1-C20-alkyl-substituted, C6-C14-aryl radical, such as p-octylphenyl, p-nonylphenyl, 2,4-dibutylphenyl, 2,4,6-triisobutylphenyl, 2,4,6-tri-n-butylphenyl or 2,4,6-tri-sec-butylphenyl, or RI, RII and RIII are identical or different (EO)w-RIV, where RIV is H or an unsubstituted or substituted C1-C30-, preferably C1-C20-, hydrocarbon radical, such as a C1-, C2-, C3-, C4-, C5- C6-, C8-, C10-, C12-, C13- (for example isotridecyl-), C14-, C16-, C18-, C20-alkyl radical, -alkenyl radical or -alkynyl radical, or an unsubstituted or substituted, for example mono- or poly-C1-C20-alkyl-substituted, C6-C14-aryl radical, such as p-octylphenyl, p-nonylphenyl, 2,4-dibutylphenyl, 2,4,6-triisobutylphenyl, 2,4,6-tri-n-butylphenyl or 2,4,6-tri-sec-butylphenyl, and w is an integer from 1 to 50, Xxe2x8ax96 being an anion.
Particular preference is given to surfactants of the formula (II) in which the sum (x+y+z) is 11-80, preferably 12-50,
R4 is (C8-C18)-alkoxy, (C8-C18)-alkenyloxy or (C8-C18)-alkynyloxy, (C7-C17)-alkylcarbonyloxy, (C7-C17)-alkenylcarbonyloxy, (C7-C17)-alkynylcarbonyloxy or (C1-C10)-alkylphenoxy, such as octylphenoxy, p-nonylphenoxy, 2,4,6-tri-n-butylphenoxy, 2,4,6-triisobutylphenoxy or 2,4,6-tric-sec-butylphenoxy, and
R5 is H, (C1-C8)-, preferably (C1-C6)-, alkyl, (C2-C18)-, preferably (C2-C6)-, alkenyl or (C2-C18)-, preferably (C2-C6)-, alkynyl, COxe2x80x94H, COxe2x80x94(C1-C17)-alkyl, COxe2x80x94(C2-C17)-alkenyl or CO-(C2-C17)-alkynyl.
Sufactants B), for example of the formula (II), are known from the literature, for example from McCutcheon""s Emulsifiers and Detergents 1994, Vol. 1: North American Edition and Vol. 2, International Edition; McCutcheon Division, Glen Rock N.J., USA and from xe2x80x9cSurfactants in Consumer Productsxe2x80x9d, J. Falbe, Springer-Verlag Berlin, 1987. The Surfactants B) mentioned in these publications are expressly incorporated Herein by way of reference. Moreover, surfactants B), for example of the formula (II), are also commercially available, for example under the trade names Genapol(copyright) X- or O- or T-series, Sapogenat(copyright) T-series, Arkopol(copyright) N-series, Afilan(copyright) PTU, Hordaphos(copyright) and Emulsogen(copyright)-series from Clariant AG; Agrilan(copyright)-types from Akcros Organics; Alkamul(copyright) and Antarox(copyright)-types from Rhodia; Emulan(copyright)-types (NP, OC, OG, OK) from BASF AG; Dehydol(copyright)-types from Henkel; Agent W(copyright)-types from Stepan Company; Crodamel(copyright)-types from Croda GmbH. The surfactants B) mentioned in the respective product leaflets are expressly incorporated herein by way of reference.
Examples of surfactants B), for example of the formula (II), are listed in table 1 below:
The sulfonylureas of the formula (I) can form salts in which the hydrogen of the xe2x80x94SO2xe2x80x94NHxe2x80x94 group is replaced by an agriculturally suitable cation. Examples of these salts are metal salts, in particular alkali metal salts (for example sodium or potassium salts) or alkaline earth metal salts, or else ammonium salts or salts with organic amines. Salt formation can also take place by addition of a strong acid to the heterocycle moiety of the compounds of the formula (I). Acids which are suitable for this purpose are, for example, HCl, HNO3, trichloroacetic acid, acetic acid or palmitic acid. Especially advantageous compounds are those in which the salt of the herbicide of the formula (I) is formed by replacing the hydrogen of the xe2x80x94SO2xe2x80x94NHxe2x80x94 group by a cation selected, for example, from the group consisting of the alkali metals, alkaline earth metals and ammonium ions, preferably sodium or tetrabutylammonium.
If the sulfonylureas of the formula (I) and/or their salts contain one or more asymmetric carbon atoms or else double bonds which are not specifically mentioned in the formula, these are still encompassed by the formula (I). The stereoisomers which are possible and which are defined by their specific spatial shape, such as enantiomers, diastereoisomers, Z- and E- isomers, are all encompassed by the formula (I) and can be obtained by customary methods from mixtures of the stereoisomers or else prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials. The abovementioned stereoisomers in pure form and also their mixtures can thus be employed in accordance with the invention.
Sulfonylureas of the formula (I) and their salts are known in principle (see, for example, EP-A-342 569, EP-A-574 418, EP-A-723 534 and EP-A-757 679, which are expressly incorporated herein by way of reference); however, the fact that they are outstandingly suitable for use as combination partners in mixtures with surfactants B) is not evident from the prior art.
Preference is given to sulfonylureas of the formula (I) and/or salts thereof in which
a) R1 is COxe2x80x94(C1-C4-alkoxy) and R2 is halogen, preferably iodine, or R2 is CH2xe2x80x94NHRe, where Re is an acyl radical, preferably C1-C4-alkylsulfonyl, or
b) R1 is COxe2x80x94Nxe2x80x94(C1-C4-alkyl)2 and R2 is NHRe, where Re is an acyl radical, preferably formyl, or
c) R1 is C2-C4-alkoxy and R2 is H.
Preference is also given to sulfonylureas of the general formula (I) and/or salts thereof in which the radical R2 is in the position para to the radical R1.
Examples of compounds of the formula (I) and/or their salts which may be mentioned are:
A1=N-(4,6-dimethoxypyrimid in-2-ylaminocarbonyl)-2-methoxycarbonyl-5-acetylaminobenzenesulfonamide
A2=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-formyl-N-methylaminomethyl)benzenesulfonamide sodium salt
A3=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-acetylamino)benzenesulfonamide sodium salt
A4=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-methyl-N-propionylamino)benzenesulfonamide sodium salt
A5=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-isopropionylmethylamino)benzenesulfonamide sodium salt
A6=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-methoxycarbonylaminomethyl)benzenesulfonamide sodium salt
A7=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N ,N-dimethylaminocarbonyl)-5-(N-methoxycarbonylamino)benzene-sulfonamide sodium salt
A8=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-formylamino)benzenesulfonamide (foramsulfuron)
A9=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-propionylamino)benzenesulfonamide sodium salt
A10=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-methylsulfonylaminomethyl)benzenesulfonamide sodium salt (mesosulfuronmethyl-sodium)
A11=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-methylsulfonylaminomethyl)benzenesulfonamide (mesosulfuron-methyl)
A12=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-methoxycarbonylaminomethyl)benzenesulfonamide sodium salt
A13=N-(4-methoxy-6-methyl-1,3,5-triazin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-iodobenzenesulfonamide (iodosulfuron-methyl)
A14=N-(4-methoxy-6-methyl-1,3,5-triazin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-iodobenzenesulfonamide sodium salt (iodo-sulfuron-methyl-sodium)
A15=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-methoxycarbonyl-5-(N-methylsulfonyl-N-methylaminomethyl)benzenesulfonamide
A16=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-ethoxybenzene-sulfonamide (ethoxysulfuron)
A17=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-ethoxybenzene-sulfonamide sodium salt (ethoxysulfuron-sodium)
A18=N-(4,6-dimethoxypyrimidin-2-ylaminocarbonyl)-2-(N,N-dimethylaminocarbonyl)-5-(N-formylamino)benzenesulfonamide sodium salt (foramsulfuron-sodium)
As component A), it is also possible to use mixtures of two or more sulfonylureas of the formula (I) and/or their salts. Examples of such mixtures are mixtures of two or more of the compounds A1 to A15 mentioned above, such as A8+A13, A8+A14, A10+A13, A10+A14, A11+A13or A11+A14.
An acyl radical for the purpose of the present description means the radical of an organic acid which is formed formally by eliminating an OH group from the organic acid, for example the radical of a carboxylic acid and radicals of acids derived therefrom, such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the radicals of carbonic monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
An acyl radical is preferably formyl or acyl selected from the group consisting of COxe2x80x94Rz, CSxe2x80x94Rz, COxe2x80x94ORz, CSxe2x80x94ORz, CSxe2x80x94SRz, SORz and SO2Rz, where Rz is in each case a C1-C10-hydrocarbon radical such as C1-C10-alkyl or C6-C10-aryl which is unsubstituted or substituted, for example by one or more substituents selected from the group consisting of halogen, such as F, Cl, Br, I, alkoxy, haloalkoxy, hydroxyl, amino, nitro, cyano or alkylthio, or Rz is aminocarbonyl or aminosulfonyl, the two last-mentioned radicals being unsubstituted, N-monosubstituted or N,N-disubstituted, for example by substituents selected from the group consisting of alkyl and aryl.
Acyl is, for example, formyl, haloalkylcarbonyl, alkylcarbonyl such as (C1-C4)-alkylcarbonyl, phenylcarbonyl, it being possible for the phenyl ring to be substituted, or is alkyloxycarbonyl, such as (C1-C4)-alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, such as (C1-C4)-alkylsulfonyl, alkylsulfinyl, such as (C1-C4)-alkylsulfinyl, N-alkyl-1-amino-alkyl, such as Nxe2x80x94(C1-C4)-alkyl-1-amino-(C1-C4)-alkyl and other radicals of organic acids.
Carbon-containing radicals are organic radicals which contain at least one carbon atom, preferably 1 to 40 carbon atoms, particularly preferably 1 to 30 carbon atoms, very particularly preferably 1 to 20 carbon atoms, and furthermore at least one atom of one or more other elements of the Periodic Table of the Elements, such as H, Si, N, P, O, S, F, CI, Br or I. Examples of carbon-containing radicals are unsubstituted or substituted hydrocarbon radicals which may be attached directly or via a heteroatom such as Si, N, S, P or O to the skeleton, unsubstituted or substituted heterocyclyl radicals which may be attached directly or via a heteroatom such as Si, N, S, P or O to the skeleton, carbon-containing acyl radicals or cyano.
The term heteroatom is to be understood as meaning elements of the Periodic Table of the Elements different from carbon and hydrogen, for example Si, N, S, P, O, F, CI, Br or I.
Hydrocarbon(oxy) radicals are straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon(oxy) radicals, for example alkyl, alkenyl, alkynyl, -cycloalkyl, cycloalkenyl or aryl and the hydrocarbonoxy radicals which correspond to these hydrocarbon radicals, such as alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy or aryloxy; aryl is a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pantalenyl, fluorenyl and the like, preferably phenyl; a hydrocarbon radical is preferably alkyl, alkenyl or alkynyl having 1 to 30 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.
Substituted radicals, such as substituted hydrocarbon(oxy) radicals, for example substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl, and the hydrocarbonoxy radicals which correspond to these hydrocarbon radicals, such as alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy or aryloxy, or substituted heterocyclyl radicals, denote, for example, a substituted radical derived from the unsubstituted skeleton, the substituents being, for example, one or more, preferably 1, 2 or 3, radicals selected from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl, and unsaturated aliphatic radicals which correspond to the saturated hydrocarbon-containing radicals mentioned, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy, etc. In the case of radicals having carbon atoms, preference is given to those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. Preference is generally given to substituents selected from the group consisting of halogen, for example fluorine and chlorine, (C1-C4)-alkyl, preferably methyl or ethyl, (C1-C4)-haloalkyl, preferably trifluoromethyl, (C1-C4)-alkoxy, preferably methoxy or ethoxy, (C1 -C4)-haloalkoxy, nitro and cyano. Particular preference is given here to the substituents methyl, methoxy and chlorine. Cycloalkyl is a carbocyclic saturated ring system, preferably with 3-6 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
The carbon-containing radicals such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and/or substituted radicals can in each case be straight-chain or branched in the carbon skeleton. Unless otherwise specified, in the case of these radicals, the lower carbon skeletons, for example those having 1 to 6 carbon atoms and, in the case of unsaturated groups, having 2 to 6 carbon atoms are preferred. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl and the like, are, for example, methyl, ethyl, n- or isopropyl, n-, iso-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, isohexyl and 1,3-dimethylbutyl, heptyls, such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meanings of the possible unsaturated radicals which correspond to the alkyl radicals; alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl.
A heterocyclic radical or ring (heterocyclyl radical) can be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; it preferably contains one or more heteroatoms in the ring, preferably selected from the group consisting of N, O and S; it is preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms. The heterocyclic radical can, for example, be a heteroaromatic radical or ring (heteroaryl), such as, for example, a mono-, bi- or polycyclic aromatic system in which at least one ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or it is a partially or fully hydrogenated radical such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, tetrahydrofuryl. Suitable substituents for a substituted heterocyclic radical are the abovementioned substituents and additionally also oxo. The oxo group can also be present on the hetero ring atoms which may exist in different oxidation states, for example in the case of N and S.
Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl and alkynyl, respectively, which are partially or fully substituted by halogen, preferably by fluorine, chlorine, and/or bromine, in particular by fluorine or chlorine, for example CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2, CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2Cl; this applies correspondingly for haloalkenyl and other halogen-substituted radicals.
The herbicidal compositions according to the invention comprising compounds of the formula (I) and/or their salts and surfactants B) have excellent herbicidal activity and, in a preferred embodiment, superadditive effects. Owing to the improved control of harmful plants by the herbicidal compositions according to the invention, it is possible to reduce the application rate and/or to increase the safety margin. Both make sense, from an economical and an ecological point of view. The amounts of A)+B) to be employed and the ratio of the components A):B) depend on a whole range of factors.
In a preferred embodiment, the herbicidal compositions according to the invention are characterized in that they have a synergistically effective amount of a combination of the compounds of the formula (I) and/or their salts with surfactants B). Here, it has to be emphasized in particular that even in combinations where the application rates or weight ratios of A):B) are such that a synergism cannot be demonstrated clearly in each casexe2x80x94for example owing to the fact that the individual compounds are usually employed in the combination in very different application rates or else because the control of harmful plants by the individual compounds is already very goodxe2x80x94a synergistic action is generally inherent to the herbicidal compositions of the invention.
Components A) and B) of the herbicidal compositions according to the invention can be formulated separately or applied by the tank mix method, or they can be contained together in a ready-to-use formulation which can then be applied in a customary manner, for example in the form of a spray liquor.
The herbicidal compositions according to the invention can be formulated in various ways depending on the prevailing biological and/or physico-chemical parameters. Examples of suitable formulation options are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates (SL), emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), granules for broadcasting and soil application, granules (GR) in the form of microgranules, spray granules, coating granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in Winnacker-Kxc3xcchler, xe2x80x9cChemische Technologiexe2x80x9d [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Edition 1986, Wade van Valkenburg, xe2x80x9cPesticide Formulationsxe2x80x9d, Marcel Dekker, N.Y., 1973; K. Martens, xe2x80x9cSpray Dryingxe2x80x9d Handbook, 3rd Ed. 1979, G. Goodwin Ltd., London.
The necessary formulation auxiliaries, such as inert materials, surfactants, solvents and other additives, are likewise known and are described, for example, in: Watkins, xe2x80x9cHandbook of Insecticide Dust Diluents and Carriersxe2x80x9d, 2nd Ed., Darland Books, Caldwell N.J., H. v. Olphen, xe2x80x9cIntroduction to Clay Colloid Chemistryxe2x80x9d, 2nd Ed., J. Wiley and Sons, N.Y.; C. Marsden, xe2x80x9cSolvents Guidexe2x80x9d, 2nd Ed., Interscience, N.Y. 1963; McCutcheon""s xe2x80x9cDetergents and Emulsifiers Annualxe2x80x9d, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, xe2x80x9cEncyclopedia of Surface Active Agentsxe2x80x9d, Chem. Publ. Co. Inc., N.Y. 1964; Schxc3x6nfeldt, xe2x80x9cGrenzflxc3xa4chenaktive xc3x84thylenoxidadduktexe2x80x9d[Surface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kxc3xcchler, xe2x80x9cChemische Technologiexe2x80x9d, Volume 7, C. Hauser Verlag Munich, 4th Edition 1986.
Based on these formulations it is also possible to produce combinations with other agrochemically active compounds which differ from component A), such as insecticides, acaricides, herbicides, fungicides, safeners, fertilizers such as ammonium sulfate, ammonium hydrogen sulfate, urea or mixtures thereof, and/or growth regulators, for example in the form of a ready-to-use formulation or as tank mix.
Wettable powders are preparations which are uniformly dispersible in water and which contain, in addition to the active compound A) and/or the surfactant B), and in addition to a diluent or inert substance, also surfactants of ionic and/or nonionic nature which are different from surfactant B) (wetting agents, dispersants), for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzene-sulfonates, sodium lignosulfonate, sodium 2,2xe2x80x2-dinaphthylmethane-6,6xe2x80x2-disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurinate. To prepare the wettable powders, the herbicidally active compounds A) and/or surfactants B) are finely ground, for example in customary apparatus such as hammer mills, fan mills and air-jet mills, and are mixed simultaneously or subsequently with the formulation auxiliaries.
Emulsifiable concentrates are prepared by dissolving the active compound A) and/or the surfactant B) in an organic solvent, for example 3-methoxypropanol, mono-, di- or oligoesters such as dimethyl malonate, dimethyl succinate, dimethyl glutarate or dimethyl adipate, butanol, cyclohexanone, dimethylformamide, xylene or else relatively high-boiling aromatic compounds, oils (such as soya oil methyl ester or rapeseed oil methyl ester) or hydrocarbons or mixtures of the organic solvents with addition of one or more surfactants of ionic and/or nonionic nature differing from surfactant B) (emulsifiers). Suitable for use as emulsifiers are, for example: calcium alkylarylsulfonates, such as calcium dodecylbenzene-sulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters (for example Atplus(copyright) 309F from Uniquema) or else block copolymers, for example based on ethylene oxide and propylene oxide.
Water-soluble concentrates are obtained, for example, by dissolving the active compound A) and/or the surfactant B) in water or a water-miscible solvent and adding, if appropriate, further auxiliaries such as water-soluble surfactants.
Dusts are obtained by grinding the active compound A) and/or the surfactant B) with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspension concentrates can be water- or oil-based. They can be prepared, for example, by wet milling using commercially customary bead mills, with or without the addition of surfactants different from surfactant B), as already mentioned above, for example, in the case of the other formulation types.
Emulsions, for example oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and, if appropriate, surfactants different from surfactant B), as already mentioned above, for example, in the case of the other formulation types.
Granules can be prepared either by spraying the active compound A) and/or surfactant B) onto adsorptive, granulated inert material or by applying active-compound concentrates to the surface of carriers such as sand, kaolinites or granulated inert material, by means of adhesive binders, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils. Suitable active compounds A) and/or surfactants B) can also be granulated in the manner which is customary for the preparation of fertilizer granulesxe2x80x94if desired as a mixture with fertilizers.
Water-dispersible granules are generally prepared by the customary processes, such as spray-drying, fluidized-bed granulation, disk granulation, mixing using high-speed mixers, and extrusion without solid inert material.
For the preparation of disk, fluidized-bed, extruder and spray granules, see, for example, processes in xe2x80x9cSpray-Drying Handbookxe2x80x9d, 3rd Ed. 1979, G. Goodwin Ltd., London; J. E. Browning, xe2x80x9cAgglomerationxe2x80x9d, Chemical and Engineering 1967, pages 147 ff.; xe2x80x9cPerry""s Chemical Engineer""s Handbookxe2x80x9d, 5th Ed., McGraw-Hill, N.Y. 1973, pp. 8-57.
For further details on the formulation of crop protection products, see, for example, G. C. Klingman, xe2x80x9cWeed Control as a Sciencexe2x80x9d, John Wiley and Sons, Inc., N.Y., 1961, pages 81-96 and J. D. Freyer, S. A. Evans, xe2x80x9cWeed Control Handbookxe2x80x9d, 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.
The herbicidal compositions according to the invention generally comprise from 0.01 to 99% by weight, in particular from 0.1 to 95% by weight, of one or more sulfonylureas of the formula (I) and/or their salts.
In wettable powders, the concentration of active compound is, for example, from about 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation constituents and, if appropriate, surfactants B). In emulsifiable concentrates, the concentration of active compound can be from about 1 to 90, preferably from 5 to 80, % by weight. Formulations in the form of dusts comprise from 1 to 30% by weight of active compound, preferably most commonly from 5 to 20% by weight of active compound, while sprayable solutions comprise from about 0.05 to 80, preferably from 2 to 50, % by weight of active compound. In the case of water-dispersible granules, the content of active compound depends partly on whether the active compound is in liquid or solid form and on the granulation auxiliaries, fillers, etc., that are used. In water-dispersible granules the content of active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
In addition, said formulations of active compound may comprise the auxiliaries such as tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, adjuvants such as mineral or vegetable oils and derivatives thereof, evaporation inhibitors and pH and viscosity regulators which are customary in each case.
The herbicidal compositions according to the invention can be prepared by customary processes, for example by mixing the components with the aid of stirrers, shakers or (static) mixers.
In a preferred embodiment of this invention, the formulations comprising sulfonylureas of the formula (I) and/or their salts are mixed in the spray tank with surfactants B) and/or formulations thereof. To this end, the sulfonylureas of the formula (I) and/or their salts can be formulated, for example on the basis of kaolin, as water-dispersible granules, where the content of sulfonylureas of the formula (I) and/or their salts may vary within wide limits between 0.01 and 99% by weight, preferably between 0.5 and 80% by weight. In addition to the sulfonylureas of the formula (I) and/or their salts, these formulations may comprise further agrochemically active compounds, such as safeners, for example in an amount of from 0.1 to 50% by weight, preferably from 0.5 to 40% by weight. The surfactants B) can be added as pure substances or in formulated form, preferably as a liquid product, such as a water-soluble concentrate or an emulsifiable concentrate.
Ready-to-use formulations can be obtained by preparing, for example, emulsifiable concentrates or oil dispersions of sulfonylureas of the formula (I) and/or their salts, surfactants B)-and further auxiliaries. In the ready-to-use formulations, the amount of sulfonylureas of the formula (I) and/or their salts can vary within wide limits and is generally between 0.01 and 99% by weight, preferably between 0.1 and 60% by weight. The amount of surfactants B) can also vary within wide limits and is generally between 1 and 80% by weight, as a rule between 5 and 50% by weight. Finally, the ready-to-use formulations may also comprise further agrochemically active compounds such as safeners, for example in an amount of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight.
If appropriate, the formulations may comprise auxiliaries such as solvents, for example aromatic solvents, such as xylenes or mixtures of aromatic compounds from the Solvesso(copyright) series such as Solvesso(copyright) 100, Solvesso(copyright) 150 or Solvesso(copyright) 200 from Exxon; aliphatic or isoparaffinic solvents, such as products from the Exxol(copyright)-D or Isopur(copyright) series from Exxon; oils of vegetable or animal origin and derivatives thereof, such as rapeseed oils or rapeseed oil methyl esters; esters, such as butyl acetate; ethers, such as diethyl ether, THF or dioxane. The solvent content is preferably 1-95% by weight, particularly preferably 5-80% by weight. Further suitable auxiliaries are, for example, emulsifiers (preferred content: 0.1-10% by weight), dispersants (preferred content: 0.1-10% by weight) and thickeners (preferred content: 0.1-5% by weight), and, if appropriate, stabilizers, such as antifoams, water scavengers, acid scavengers and crystallization inhibitors.
The herbicidal compositions according to the invention can be used pre- or post-emergence, for example by spraying. The use of the mixtures allows the amount of preparation required for controlling weeds to be reduced considerably.
The surfactants B) to be used according to the invention are generally applied together with the sulfonylurea(s) A) or immediately afterward, preferably in the form of a spray liquor which comprises effective amounts of surfactants B) and sulfonylureas A) and, if appropriate, further customary auxiliaries. The spray liquor is preferably prepared based on water and/or an oil, for example a high-boiling hydrocarbon such as kerosene or paraffin. Here, the herbicidal compositions according to the invention can be realized as a tank mix or via a xe2x80x9cready-to-use formulationxe2x80x9d.
The weight ratio of sulfonylurea A) to surfactant B) can vary within a wide range and depends, for example, on the efficacy of the sulfonylurea. It is generally in a range of from 10:1 to 1:5000, preferably from 4:1 to 1:2000.
The application rates of the compound(s) of the formula (I) and/or their salts are generally between 0.1 and 200 g of AS/ha (AS=active substance, i.e. application rate based on the active compound), preferably between 0.5 and 100 g of ai/ha. The application rates of surfactants B) are generally between 1 and 5000 g of surfactant/ha; preference is given to from 10 to 2000 g of surfactant/ha.
The concentration of the surfactants B) to be used according to the invention in a spray liquor is generally from 0.05 to 4% by weight, preferably 0.1 to 1% by weight, in particular from 0.1 to 0.3% by weight, of surfactant.
The herbicidal compositions according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. The active compounds also act efficiently on perennial weeds which produce shoots from rhizomes, root stocks or other perennial organs and which are difficult to control. In this context, it is generally immaterial whether the substances are applied pre-sowing, pre-emergence or post-emergence. Specifically, examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the herbicidal compositions according to the invention, without these being a restriction to certain species.
Examples of weed species on which the active compounds act efficiently are, from amongst the monocotyledons, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and also Cyperus species mainly from the annual sector and, from amongst the perennial species, Agropyron, Cynodon, Imperata and Sorghum, and also perennial Cyperus species.
In the case of the dicotyledonous weed species, the spectrum of action extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida from amongst the annuals, and Convolvulus, Cirsium, Rumex and Artemisia in the case of the perennial weeds.
The compositions according to the invention also effect outstanding control of harmful plants which occur under the specific conditions of rice-growing such as, for example, Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus.
If the herbicidal compositions according to the invention are applied to the soil surface prior to germination, then the weed seedlings are either prevented completely from emerging, or the weeds grow until they have reached the cotyledon stage but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.
If the herbicidal compositions according to the invention are applied post-emergence to the green parts of the plants, growth also stops drastically a very short time after the treatment and the weed plants remain at the developmental stage of the point in time of application, or they die completely after a certain time, so that in this manner competition from the weeds, which is harmful to the crop plants, is eliminated at a very early point in time and in a sustained manner.
Although the herbicidal compositions according to the invention have an excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, for example dicotyledonous crops such as soya, cotton, oilseed rape, sugar beet, in particular soya, or gramineous crops such as wheat, barley, rye, rice or corn, are not damaged at all, or only to a negligible extent. For these reasons, the present compounds are highly suitable for selectively controlling undesired plant growth in plantings of agriculturally useful plants including ornamental plants.
In addition, the herbicidal compositions according to the invention have outstanding growth-regulating properties in crop plants. They engage in the plant metabolism in a regulating manner and can thus be employed for the targeted control of plant constituents and for facilitating harvesting, such as for example by provoking desiccation and stunted growth. Furthermore, they are also suitable for generally regulating and inhibiting undesirable vegetative growth, without destroying the plants in the process. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops because lodging can be reduced hereby, or prevented completely.
Owing to their herbicidal and plant-growth-regulatory properties, the herbicidal compositions according to the invention can also be employed for controlling harmful plants in crops of known or still to be developed genetically engineered plants. The transgenic plants generally have particularly advantageous properties, for example resistance to certain pesticides, in-particular certain herbicides, resistance to plant diseases or causative organisms of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses.
Other particular properties relate, for example, to the quantity, quality, storage stability, composition and to specific ingredients of the harvested product. Thus, transgenic plants having an increased starch content or a modified quality of the starch or those having a different fatty acid composition of the harvested product are known.
The use of the compositions according to the invention in economically important transgenic crops of useful and ornamental plants, for example of cereals, such as wheat, barley, rye, oats, millet, rice, manioc and corn, or else in crops of sugar beet, cotton, soya, oilseed rape, potato, tomato, pea and other vegetable species is preferred. The compositions according to the invention can preferably be used as herbicides in crops of useful plants which are resistant or which have been made resistant by genetic engineering toward the phytotoxic effects of the herbicides.
When using the herbicidal compositions according to the invention in transgenic crops, in addition to the effects against harmful plants which can be observed in other crops, there are frequently effects which are specific for the application in the respective transgenic crop, for example a modified or specifically broadened spectrum of weeds which can be controlled, modified application rates which can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and an effect on the growth and the yield of the transgenic crop plants.
The invention therefore also provides for the use of the compositions according to the invention as herbicides for controlling harmful plants, preferably in crop plants, where the crop plants may also be transgenic crop plants.
The herbicidal compositions according to the invention can also be used in a non-selective manner for controlling undesirable vegetation, for example on paths, open spaces, industrial sites or rail tracks.
Owing to the relatively low application rate of the herbicidal compositions according to the invention, they are, as a rule, already well tolerated. In particular, the combinations according to the invention lead to a reduction in the absolute application rate in comparison with the individual application of a herbicidal active compound.
If, if desired, the tolerance and/or selectivity of the herbicidal compositions according to the invention are to be increased further, it may be advantageous to apply them jointly as a mixture or staggered in time one after the other together with safeners or antidotes.
Compounds which are suitable as safeners or antidotes for the herbicidal compositions according to the invention are disclosed, for example, in EP-A-333 131 (ZA-89/1960), EP-A-269 806 (U.S. Pat. No. 4,891,057), EP-A-346 620 (AU-A-89/34951) and the international patent applications PCT/EP 90/01966 (WO-91108202) and PCT/EP 90102020 (WO-911078474) and the literature cited therein or can be prepared by the processes described therein. Other suitable safeners are known from EP-A-94 349 (U.S. Pat. No. 4,902,304), EP-A-191 736 (U.S. Pat. No. 4,881,966) and EP-A-0 492 366 and the literature cited therein.
In a preferred embodiment, the herbicidal compositions of the present invention therefore additionally comprise C) of one or more compounds which act as safeners or antidotes.
Preferred antidotes or safeners or groups of compounds which are suitable as safeners or antidotes in the herbicidal compositions of the invention are, inter alia:
a) Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type, preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (compound C1-1, mefenpyr-diethyl) and related compounds as they are described in the international application WO 91/07874 (PCT/EP 90102020);
b) Dichlorophenylpyrazolecarboxylic acid derivatives, preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (compound C1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (compound C1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (compound C1-4), ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (compound C1-5) and related compounds as are described in EP-A-0 333 131 and EP-A-0 269 806;
c) Compounds of the triazolecarboxylic acid type, preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate (compound C1-6, fenchlorazole-ethyl) and related compounds (see EP-A-0 174 562 and EP-A-0 346 620);
d) Compounds of the dichlorobenzyl-2-isoxazoline-3-carboxylic acid type, compounds of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid type, preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (compound C1-7) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (compound C1-8) and related compounds as they are described in the international patent application WO 91/08202 (PCT/EP 90/01966);
e) Compounds of the 8-quinolinoxyacetic acid type, preferably compounds such as 1-methylhex-1-yl 5-chloro-8-quinolinoxyacetate (cloquintocet-mexyl, C2-1), 1,3-dimethylbut-1-yl 5-chloro-8-quinolin-oxyacetate (C2-2), 4-allyloxybutyl 5-chloro-8-quinolinoxyacetate (C2-3), 1-allyloxyprop-2-yl 5-chloro-8-quinolinoxyacetate (C2-4), ethyl 5-chloro-8-quinolinoxyacetate (C2-5), methyl 5-chloro-8-quinolinoxyacetate (C2-6), allyl 5-chloro-8-quinolinoxyacetate (C2-7), 2-(2-propylidene-iminooxy)-1-ethyl 5-chloro-8-quinolinoxy-acetate (C2-8), 2-oxoprop-1-yl 5-chloro-8-quinolinoxyacetate (C2-9) and related compounds as they are described in EP-A-0 086 750, EP-A-0 094 349 and EP-A-0 191 736 or EP-A-0 492 366;
f) Compounds of the 5-chloro-8-quinolinoxymalonic acid type, preferably compounds such as diethyl 5-chloro-8-quinolinoxy-malonate, diallyl 5-chloro-8-quinolinoxymalonate, methyl ethyl 5-chloro-8-quinolinoxymalonate and related compounds as they have been described and proposed in the German patent application EP-A-0 582 198;
g) Active compounds of the type of the phenoxyacetic- or -propionic acid derivatives or of the aromatic carboxylic acids, such as, for example, 2,4-dichlorophenoxyacetic acid (and its esters) (2,4-D), 4-chloro-2-methylphenoxypropionic ester (mecoprop), MCPA or 3,6-dichloro-2-methoxybenzoic acid (and its esters) (dicamba);
h) Compounds of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid type, preferably ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (C3-1, isoxadifen-ethyl);
i) Compounds known as safeners, for example for rice, such as fenclorim (=4,6-dichloro-2-phenylpyrimidine, Pesticide Manual, 11th Edition, 1997, pp. 511-512), dimepiperate (=S-(1-methyl-1-phenylethyl) 1-piperidinecarbothioate, Pesticide Manual, 11th Edition, 1997, pp. 404-405), daimuron (=1-(1-methyl-1-phenylethyl)-3-p-tolylurea, Pesticide Manual, 11th Edition, 1997, p. 330), cumyluron (=3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenyl-ethyl)urea, JP-A-601087254), methoxyphenone (=3,3xe2x80x2-dimethyl-4-methoxybenzophenone), CSB (=1-bromo-4-(chloromethyl-sulfonyl)benzene, CAS Reg. No. 54091-06-4).
In addition, at least some of the compounds mentioned are described in EP-A-0 640 587, which is herewith referred to for publication purposes.
j) A further important group of compounds which are suitable as safeners and antidotes is disclosed in WO 95107897.
The safeners (antidotes) of the above groups a) to j) reduce or contain phytotoxic effects which may occur in crops of useful plants when employing the herbicidal compositions according to the invention without adversely affecting the efficacy of the herbicides against harmful plants. This allows the field of application of the herbicidal compositions according to the invention to be widened considerably, and, in particular, the use of safeners allows combinations to be employed whose use has previously only been possible with limitations or with insufficient success, i.e. combinations which, without safeners, had a poor spectrum of action and led to insufficient control of harmful plants when applied at low dosage rates.
The herbicidal compositions according to the invention and the abovementioned safeners can be applied together (as a ready-to-use formulation or by the tank mix method) or in succession in an arbitrary sequence. The weight ratio of safener:herbicide (compound(s) of the formula (I) and/or the salts thereof) may vary within wide limits and is preferably in the range of 1:100 to 100:1, in particular 1:10 to 10:1. The amounts of herbicide(s) and safener(s) which are optimal in each case depend usually on the type of the herbicidal composition and/or on the safener used and on the nature of the plant stand to be treated.
Depending on their properties, the safeners of type C) may be used for pretreating the seed of the crop plant (seed dressing) or incorporated into the seed furrow prior to sowing or applied together with the herbicide mix before or after emergence of the plants.
The pre-emergence treatment includes not only the treatment of the area under cultivation before sowing, but also the treatment of the areas under cultivation where seed has been sown but the plants have not yet emerged. The joint application together with the herbicide mix is preferred. To this end, tank mixes or ready-to-use formulations may be employed.
The required application rates of the safeners may vary within wide limits, depending on the indication and the herbicide used, and are, as a rule, in the range of 0.001 to 1 kg, preferably 0.005 to 0.2 kg, of active compound per hectare.
The present invention also relates to a method of controlling undesired plants, preferably in crop plants, which comprises applying a herbicidally active amount of the herbicidal composition according to the invention, for example to the plants, the parts of the plants, the seeds of the plants or the area under cultivation.
In a preferred variant of the method the herbicidal compositions according to the invention are applied in the form of tank mixes, the individual components, for example in the form of formulations, jointly being mixed in the tank with water or an oil liquor and the resulting spray mixture being applied. Since the crop plant tolerance of the combinations according to the invention is decidedly good while simultaneously effecting very good control of the harmful plants, the combinations can be considered as selective. In a preferred modification of the method, herbicidal compositions are therefore employed for the selective control of undesired plants.
The herbicidal compositions according to the invention can be applied in the customary manner, for example with water and/or oil as carrier in amounts of approximately 0.5-4000, preferably 100 to 1000, liters of spray liquor/ha. The compositions may also be applied by the low-volume and ultra-low-volume (ULV) methods and in the form of granules and microgranules.
A preferred application relates to the use of herbicidal compositions which comprise components A and B in a synergistically effective amount.
The invention also includes herbicidal compositions which comprise mixtures of one or more combination partners A), preferably A8, A10, A11, A13, A14, A16, A17 and/or A18 and one or more combination partners B), if appropriate in combination with one or more safeners C).
Preferred examples of the herbicidal compositions according to the invention which may be mentioned are the following combinations of A8, A10, A11, A13, A14, A16, A17 and/or A18 with surfactants B), without the combinations being limited to those mentioned explicitly:
A8 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A10 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A11 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A13 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A14 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A16 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A17 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A18 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A8+A13 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A8+A14 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A11+A13 in combination with one of the surfactants of group B1 to B105 (see Table 1)
A11+A14 in combination with one of the surfactants of group B1 to B105 (see Table 1)
In the combinations listed, it may be advantageous to use a safener, as this may reduce possible damage to the crop plant caused by sulfonylurea derivatives or other herbicidally active compounds.
In addition, the herbicidal compositions of the present invention may comprise, to round off the properties, additionally, in most cases in minor amounts, one, two or more agrochemically active compounds differing from component A) (for example herbicides, insecticides or fungicides).
Thus, there are numerous possibilities of combining a plurality of active compounds with one another and using them jointly for controlling harmful plants, preferably in crop plants, without deviating from the essence of the invention.
To summarize, it can be said that, when sulfonylureas of the formula (I) and/or their salts are used together with one or more surfactants B), an excellent herbicidal activity is obtained. The activity of the herbicidal compositions according to the invention in a preferred embodiment is more pronounced than the activity of the individual components employed when used on their own.
These effects permit, inter alia, a reduction of the application rate, the control of a broader spectrum of broad-leafed weeds and weed grasses, the closure of activity gaps, also with respect to resistant species, a more rapid and safer action, a longer duration of action, a complete control of the harmful plants with only one or a few applications, and a widening of the period of use. Moreover, the herbicidal compositions according to the invention have better selectivity in crop plants.
The abovementioned properties are needed in practical control of weeds to keep agricultural crops free of undesirable competing plants and thus to secure and/or increase the quality and quantity of the yields. With respect to the described properties, the prior art is considerably surpassed by these novel combinations. In addition, the combinations according to the invention permit, in an excellent manner, the control of harmful plants which are otherwise resistant.

Abstract: in which

Abstract: R3 is H or C1-C6-alkyl,

Abstract: m is zero or 1,

Abstract: Z is CH or N, and

Abstract: B) one or more surfactants comprising as structural element at least 10 alkylene oxide units.


Disclosed is a semiconductor package characterized by having at least one cavity defined in a substrate and at least one buffer pad disposed in the at least one cavity. The semiconductor package includes a semiconductor chip disposed on the substrate, at least one conductive trace connecting with the buffer pad and at least one bonding wire electrically connecting the semiconductor chip to the buffer pad. The buffer pad has a thickness larger than the thickness of the conductive trace.

1. Field of the Invention
This invention generally relates to a semiconductor package and a substrate therefore, and more specifically to a semiconductor package and a substrate therefor which are designed for overcoming or eliminating the signal reflection issues.
2. Description of the Related Art
In today""s rapidly growing world of electronic products, there is a main tendency towards high speed circuits. One of the major issues in developing high speed circuits is how to maintain the signal integrity during the signal transmission through a line so that the correct waveform can be kept when the signal arrives the opposite terminal of the line. Otherwise, a waveform distortion may cause malfunction of the circuit, such as producing wrong output, running abnormally or being unable to work, and it makes the product become unmarketable. There are many sources for noise, and the signal reflection is one of the sources.
When a signal is transmitted through a medium, such as a copper line, a portion of the signal isn""t sent to the opposite end of the medium but is reflected toward the signal source, it is so-called xe2x80x9csignal reflectionxe2x80x9d. The reflected signal tends to interfere constructively or destructively with the original signal at different locations of the signal path thereby altering the waveform of the original signal. This causes a misinterpretation of the signal upon receiving a signal with altered waveform. Furthermore, the higher the signal speed the more critical the signal reflection problem becomes.
There are two major causes for the signal reflectionxe2x80x94one is an impedance mismatch between associated mediums (i.e., interconnecting lines), and the other is a non-linear change of the interconnecting line. Set forth below is one example of the signal reflection resulted from the xe2x80x9cnon-linear changexe2x80x9d observed in a conventional semiconductor chip package. When the signal current transmitted from a chip through a substantially vertical gold wire flows into a horizontal conductive trace on a substrate supporting the chip, the current along the vertical direction can hardly be changed to flow in the horizontal direction immediately thereby creating a discontinuity between the gold wire and the conductive trace such that a signal reflection will occur at the discontinuity. Accordingly, there exists a need in the art for a semiconductor package which overcomes, or at least reduces the signal reflection issues.
It is an object of the present invention to provide a semiconductor package utilizing a substrate which can overcome or reduce the problem of the signal reflection occurring at the contact pad on the substrate for wire bonding due to the non-linear change of the interconnecting line.
To achieve the above listed and other objects, the present invention provides a semiconductor package mainly including a substrate comprising a plurality of conductive traces, a semiconductor chip disposed on the upper surface of the substrate and a plurality of wires electrically connecting the semiconductor chip to the conductive traces of the substrate. The present invention is characterized in that the substrate has at least one cavity formed at the junction between the conductive trace on the substrate and the wire extending from the semiconductor chip. The at least one cavity is provided with at least one buffer pad which connects with the conductive trace on the substrate. The buffer pad has a thickness larger than the thickness of the conductive trace. Accordingly, when the signal current is transmitted from the chip through the wire in a substantially vertical direction to the conductive trace of the substrate, the buffer pad provides enough space for the current to change its flow in a horizontal direction thereby overcoming or at least reducing the problem of the signal reflection.
The cavity of the substrate has a depth between about one-third and about one-fifth of the thickness of the substrate and the buffer pad has a thickness substantially equal to the depth of the cavity. Both the buffer pad and the conductive trace on the substrate are made of substantially the same material (typically selected from materials which conduct electricity well, e.g., copper). Generally speaking, gold wires are chosen as the wires for electrically connecting the semiconductor chip to the conductive trace on the substrate. The buffer pad is further provided with a nickel layer formed thereon and a gold layer on the nickel layer thereby facilitating the bonding between the gold wire and the copper trace. Additionally, the substrate is further provided with a plurality of metal pads on the lower surface thereof, wherein the conductive trace is electrically connected to the metal pad by a plurality of plated via holes and to an outside circuit through a solder ball provided on the metal pad.
The present invention further provides methods of manufacturing a substrate for use in the aforementioned semiconductor package.
One method is conducted by processing a conventional substrate into the substrate suitable for use in the present invention. Steps to accomplish the method are described below. First, a substrate with a plurality of conductive traces and a solder mask is used. Next, at least one cavity is formed in the substrate by mechanical drilling or laser ablation. Then the cavity is filled with conductive material (same as the material of the conductive trace, e.g., copper) through a selectively filling step to form at least one buffer pad adapted for wire bonding to the semiconductor chip. According to one embodiment of the present invention, the selectively filling step is accomplished by the following steps. First, a first shielding layer is formed on the entire upper surface of the substrate with the at least one cavity exposed from the first shielding layer. Next, a layer of conductive material is deposited on the upper surface of the substrate by electroless plating. Then, the first shielding layer is removed from the substrate. A second shielding layer is formed on the conductive trace which is exposed from the solder mask and only the at least one cavity is exposed. Next, the cavity is filled with conductive material by electroplating. Finally, the second shielding layer is removed and the filling step is completed. Alternatively, before the second shielding layer is removed, a nickel layer may be formed on the buffer pad and a gold layer may be formed on the nickel layer.
The present invention provides another method of manufacturing a substrate for use in a semiconductor chip package. The method comprises the following steps. First, at least one cavity is formed in the upper surface of a dielectric layer and a plurality of via holes are formed through the dielectric layer by mechanical drilling or laser ablation. Next, a metal layer is formed over the entire surface of the dielectric layer including the at least one cavity and the surface of the via holes. Then, the metal layer is selectively etched to form a predetermined circuit comprising a plurality of conductive traces on the upper surface of the dielectric layer, wherein at least one conductive trace has one end covering the at least one cavity. Next, the at least one cavity is filled with conductive material (same as the material of the aforementioned metal layer) by a selectively filling step so as to form at least one buffer pad adapted for wire bonding to the semiconductor chip. According to one embodiment of the present invention, the selectively filling step is accomplished by the following steps: A layer of solder mask is formed on the entire upper surface of the dielectric layer and the conductive traces with the at least one cavity exposed from the solder mask. The cavity is filled with conductive material by electroplating. Then, the solder mask on predetermined portions (e.g., fingers or solder pads) of the conductive traces is removed. Thereafter, a nickel layer is formed on both the buffer pad and the predetermined portions of the conductive traces which are exposed from the solder mask. Finally, a gold layer is formed on the nickel layer.

Semiconductor package and substrate thereof


A drive and metering apparatus for an injection apparatus for releasing a liquid product, the drive and metering apparatus comprising: a) a housing, b) a dose adjustment member, which is rotatable relative to the housing for adjusting the product dose to be released, c) an actuation member which is displaceable from a non-actuated position, which it assumes while adjusting the product dose to be released, into an actuated position, which it assumes while it releases the product, wherein the displacement of the actuation member into the actuated position triggers a product release and the actuation member comprises an actuation section, which is accessible to a user of the drive and metering apparatus and by means of which the user can displace the actuation member from the non-actuated position into the actuated position, d) wherein the actuation section is arranged distally in relation to the dose adjustment member.

The invention concerns an injection apparatus for administration of a liquid product, especially a medicament, for example insulin for treatment of diabetes. In detail, the invention concerns a drive and metering apparatus for such an injection apparatus. The drive and metering apparatus comprises an actuation member having an actuation section, which is mounted laterally on the elongated drive and metering apparatus or injection apparatus and which does not form the rear end of the apparatus.
The term "medicament" here comprises any flowable medicinal formulation that is suitable for controlled administration through a means, for example a cannula or hollow needle, for example comprising a liquid, a solution, a gel, or a fine suspension that contains one or more medicinally active agents. Medicament can be a composition having a single active agent or a premixed or co-formulated composition having a plurality of active agents from a single container. Medicament comprises drugs like peptides (for example, insulins, insulin-containing medicaments, GLP-1-containing and derived or analogous preparations), proteins and hormones, biologically obtained or biologically active agents, agents based on hormones or genes, nutritional formulations, enzymes, and other substances, both in solid (suspended) or liquid form, and also polysaccharides, vaccines, DNA or RNA or oligonucleotides, antibodies or parts thereof, and suitable bases, adjuvants, and vehicles.
From the prior art, for example WO 2013/144020 A1, EP 2 829 292 A1, and WO 2015/081451 A1, are known injection apparatuses that have at their proximal end an actuation button, the actuation of which triggers the release of a preset product dose. From U.S. Pat. No. 5,104,380 A1, WO 02/053214 A1, and WO 2007/017052 A1 are known injection apparatuses that have a triggering member laterally mounted on the injection apparatus, the actuation of which triggers a product release.

Injection apparatus comprising a laterally attached actuation member for triggering the product release


In each sub-frame, data writing scanning is performed twice continuously, and then data erasing scanning is performed twice continuously. The applied voltage in the data writing scanning and the applied voltage in the data erasing scanning are substantially equal in magnitude, but opposite in polarity. After a response of the liquid crystal by the first application of voltage, the cell charge decreases and the responsiveness of liquid crystal decreases. However, with the second application of voltage of the same polarity, charges corresponding to the applied voltage are stored again in the liquid crystal cell, and the liquid crystal responds again. A display of a greater number of grayscales than the number of output grayscales of a driver is achieved according to a combination of magnitude of voltages to be applied to the liquid crystal a plurality of times within each sub-frame.

The present invention relates to a liquid crystal display device for displaying an image by using a liquid crystal material having spontaneous polarization and on/off driving of switching elements.
Along with the recent development of so-called information-oriented society, electronic apparatuses, such as personal computers and PDA (Personal Digital Assistants), have been widely used. With the spread of such electronic apparatuses, portable apparatuses that can be used in offices as well as outdoors have been used, and there are demands for small-size and light-weight of these apparatuses. Liquid crystal display devices are widely used as one of the means to satisfy such demands. Liquid crystal display devices not only achieve small size and light weight, but also include an indispensable technique in an attempt to achieve low power consumption in portable electronic apparatuses that are driven by batteries.
The liquid crystal display devices are mainly classified into the reflection type and the transmission type. In the reflection type liquid crystal display devices, light rays incident from the front face of a liquid crystal panel are reflected by the rear face of the liquid crystal panel, and an image is visualized by the reflected light; whereas in the transmission type liquid crystal display devices, the image is visualized by the transmitted light from a light source (back-light) placed on the rear face of the liquid crystal panel. Since the reflection type liquid crystal display devices have poor visibility because the reflected light amount varies depending on environmental conditions, transmission type color liquid crystal display devices are generally used as display devices of personal computers that display full-color images.
As the color liquid crystal display devices, TN (Twisted Nematic) type color liquid crystal display devices using switching elements such as a TFT (Thin Film Transistor) are widely used. Although the TFT-driven TN type liquid crystal display devices have better display quality compared to an STN (Super Twisted Nematic) type, they require a back-light with high intensity to achieve high screen brightness because the light transmittance of the liquid crystal panel is only 4% or so at present. For this reason, a lot of power is consumed by the back-light. Moreover, since a color display is achieved using color filters, a single pixel needs to be composed of three sub-pixels, and there are problems that it is difficult to provide a high-definition display, and the purity of the displayed colors is not sufficient.
In order to solve such problems, the present inventor et al. developed field-sequential type liquid crystal display devices (see, for example, T. Yoshihara, et. al., AM-LCD '99 Digest of Technical Papers, p. 185, 1999; T. Yoshihara, et. al., SID '00 Digest of Technical Papers, p. 1176, 2000). Since such a field-sequential type liquid crystal display device does not require sub-pixels, it is possible to easily realize a higher definition display compared to color-filter type liquid crystal display devices. Moreover, since a field-sequential type liquid crystal display device can use the color of light emitted by the light source as it is for display without using a color filter, the displayed color has excellent purity. Furthermore, since the light utilization efficiency is high, the field-sequential type liquid crystal display device has the advantage of low power consumption. However, in order to realize a field-sequential type liquid crystal display device, high-speed responsiveness (2 ms or less) of liquid crystal is essential.
In order to provide a field-sequential type liquid crystal display device with significant advantages as mentioned above or increase the speed of response of a color-filter type liquid crystal display device, the present inventor et al. are conducting research and development on the driving of liquid crystal such as a ferroelectric liquid crystal having spontaneous polarization, which may achieve 100 to 1000 times faster response compared to a prior art, by a switching element such as a TFT (Thin Film Transistor). In the ferroelectric liquid crystal, as shown in FIG. 1, with the application of voltage, the long-axis direction of the liquid crystal molecule is tilted. A liquid crystal panel sandwiching the ferroelectric liquid crystal therein is sandwiched by two polarization plates whose polarization axes are orthogonal to each other, and the intensity of the transmitted light is changed using the birefringence caused by the change in the long-axis direction of the liquid crystal molecule.
FIG. 2 shows an example of time chart of display control in a conventional field-sequential type liquid crystal display device. FIG. 2(a) shows the scanning timing of each line of the liquid crystal panel, and FIG. 2(b) shows the ON timing of red, green and blue colors of the back-light. One frame is divided into three sub-frames, and, for example, as shown in FIG. 2(b), red light is emitted in the first sub-frame, green light is emitted in the second sub-frame, and blue light is emitted in the third sub-frame.
Meanwhile, as shown in FIG. 2(a), for the liquid crystal panel, image data writing scanning and erasing scanning are performed within a sub-frame of each of red, green and blue colors, However, the timings are adjusted so that the start timing of writing scanning coincides with the start timing of each sub-frame, and the end timing of erasing scanning coincides with the end timing of each sub-frame, and the time required for each of the writing scanning and the erasing scanning is set to a half of each sub-frame. During the writing scanning and the erasing scanning, voltages corresponding to the same image data, which are equal in magnitude and different in polarity, are applied to the liquid crystal panel (see, for example, Japanese Patent Application Laid-Open No. 11-119189/1999).
Accordingly, when a voltage of one polarity is applied in the writing scanning, a bright display is provided, while, when a voltage of the other polarity is applied in the erasing scanning, a substantially black display is provided. More precisely, even after the erasing scanning, the same image as that displayed after the writing scanning is displayed with very low brightness compared to the image after the writing scanning. Note that in this specification, scanning for obtaining a display image with high brightness is called "writing scanning", while, scanning for obtaining an image with low brightness, or an image perceived as a black image, is called "erasing scanning".
A field-sequential type liquid crystal display device as described above has high light utilization efficiency and can reduce the consumption of power compared to a color-filter type liquid crystal display device. However, in the case where a ferroelectric liquid crystal is used as a liquid crystal material, since the ferroelectric liquid crystal has spontaneous polarization, if it is driven by a switching element such as a TFT, it is necessary to store charges necessary for reversing the spontaneous polarization in a liquid crystal cell through the switching element, and consequently a higher voltage is required compared to ordinary nematic liquid crystal. Moreover, a large storage capacity is necessary for storing charges. These problems also occur in a color-filter type liquid crystal display device using a ferroelectric liquid crystal, and there is a demand for a lower drive voltage. In other words, it is desired to realize a high light transmittance with a lower voltage.
On the other hand, in order to improve the display quality, there is an increasing demand for the realization of a greater number of display colors (multi-level grayscale display). However, since a liquid crystal display device employs an analog grayscale, when the number of grayscale levels is increased, the potential difference between grayscale levels decreases. Thus, from the point of view of the liquid crystal response and an output variation of the driver, there is a problem that it is difficult to achieve a multi-level grayscale display.


The present invention provides a semi-enclosed applicator for distributing a substance onto a target surface. The applicator has a first side, a second side, and an internal cavity between the first and second sides. The applicator further includes at least one opening, such that the internal cavity is externally accessible, and the applicator further comprises: (a) a substantially non-absorbent material on one of the first and second sides; (b) a substantially absorbent material on the other of the first and second sides; and (c) a substantially fluid-impervious barrier layer within the internal cavity adjacent the non-absorbent material. The present invention also provides a semi-enclosed applicator for distributing a substance onto a target surface, the applicator having a first side, a second side, and an internal cavity between the first and second sides. The applicator further includes at least one opening, such that the internal cavity is externally accessible, and the applicator further comprises: (a) a substantially fluid-impervious barrier layer within the internal cavity adjacent one of the sides; and (b) a rupturable fluid-containing reservoir located between the barrier layer and the side.

The present invention relates to a semi-enclosed applicator useful for distributing substances onto target surfaces. The present invention also relates to such an applicator that also contains a substance for application to the surface of a target object. More particularly, the present invention relates to such applicators wherein the substance may be released from the applicator material and distributed upon the surface of the target object, then removed from the surface and absorbed by the applicator.
In the art of dispensing, articles have been developed which are coated or impregnated with useful substances intended to be utilized when the article is contacted with a target surface. While there are advantages with having the substance present on or near the surface of such articles, there is often the drawback that the useful substance is unprotected and is subject to inadvertent contact before intended use. Inadvertent contact may lead to contamination of the substance, loss of the substance onto surfaces other than the desired target surface, and/or contamination of such other surfaces with the substance. Moreover, the use of such articles to manually apply a substance to a surface of an object frequently results in exposure of a user""s hands to the substance. At the very least such a scenario results in a waste of product and is undesirable from an aesthetic standpoint and, at worst, results in excessive exposure of the user to potentially harmful, toxic, or otherwise undesirable substances.
Other common approaches involve dispensing a substance such as a cleaner or protectant from a bottle or other closed vessel onto the target surface, then utilizing a sponge, towel, brush, or other implement to distribute the product on the surface and, if desired, absorb any excess product, potentially with another implement or substrate. Such practices are commonplace with surfaces such as glass, countertops, and other kitchen and bathroom surfaces. While such practices are widely accepted, they often result in inefficient use of product and/or contact with the substances involved. Moreover, utilizing such an implement typically only provides one type of material surface for use in contacting the substance and the target surface. Applying the substance to the applicator from a vessel at the point of use likewise often results in inefficient use of product and/or contact with the substances involved.
A common approach to cleaning glass or other surfaces, for example, is to spray cleaning solution onto the surface and then wipe the surface with a paper towel. Spraying the cleaning solution usually wastes some of the cleaning solution due to over-spray landing on areas not intended to be cleaned. This over-spray is often undesirable since some surfaces can be harmed by this cleaning solution or at a minimum requires additional surfaces to be cleaned. The paper towel is used to both spread the cleaning solution on the surface as well as absorbing any excess. The paper towel has a difficult time spreading the cleaning solution since it is typically designed to be highly absorbent. To compensate, a disposable paper towel can be made partially saturated making it easier to spread the cleaner. This however typically makes the towel weaker due to a paper towel""s lack of wet strength. Then a separate dry paper towel can be used to buff the glass dry and to absorb any excess cleaner. This approach requires more cleaning solution to be applied and requires more paper towels than desired. To compensate for this approach some consumers use newspaper quality paper or low absorbency paper towels. This type of paper has a lower absorbency level and naturally does a better job of spreading the cleaning solution instead of absorbing the cleaner into the paper towel. Also these types of towels have a stiffer and harder furnish which tend to aid in buffing the glass to a streak-free shine. However, this approach is less desired because special paper towels are required and a lot of buffing is required to get the desired end result.
Accordingly, it would be desirable to provide an applicator for applying a substance to a target surface that permits greater control by the user during the application process.
It would also be desirable to provide such an applicator that permits the user to apply a substance to a target surface with reduced messiness and waste of the substance.
It would further be desirable to provide such an applicator that provides multiple surfaces of diverse materials and/or multiple substances for use in multiple tasks.
The present invention provides a semi-enclosed applicator for distributing a substance onto a target surface and a method for making such an applicator. The applicator has a first side, a second side, and an internal cavity between the first and second sides. The applicator further includes at least one opening, such that the internal cavity is externally accessible, and, in a preferred embodiment, the applicator further comprises: (a) a substantially non-absorbent fibrous material on one of the first and second sides; (b) a substantially absorbent fibrous material on the other of the first and second sides; and (c) substantially fluid-impervious barrier layer within the internal cavity adjacent the non-absorbent material.
The present invention also provides a semi-enclosed applicator for distributing a substance onto a target surface, the applicator having a first side, a second side, and an internal cavity between the first and second sides. The applicator further includes at least one opening, such that the internal cavity is externally accessible, and the applicator further comprises: (a) a substantially fluid-impervious barrier layer within the internal cavity adjacent one of the sides; and (b) a rupturable fluid-containing reservoir located between the barrier layer and the side.

Semi-enclosed applicator and a cleaning composition contained therein


A new and distinct flowering Pelargonium plant with abundant red-purple colored flowers.

Botanical classification: Pelargonium crispum.
Varietal denomination: xe2x80x98Pacbicolorxe2x80x99.
The present invention comprises a new and distinct cultivar of Pelargonium crispum hybrid known by the varietal name xe2x80x98Pacbicolorxe2x80x99. The new variety was discovered in a selected breeding program in Dresden, Germany. The new variety is the result of combination breeding from a collection of proprietary breeding plants. The flower habit and size of the new variety are similar to its parents but with different flower color. The new variety was first asexually reproduced in November 2000 by cuttings in Dresden, Germany. The new variety was grown in a warm greenhouse in January; then moved outside in February; then transferred to baskets in May. The new variety has been trial and field tested in Dresden and has been found to retain its distinctive characteristics and remain true to type through successive propagations.

Variety of pelargonium plant named xe2x80x98Pacbicolorxe2x80x99


A table and seating arrangement includes a table and seats positioned along at least one edge of the table. The seats define a cavity, at least a portion of the cavity having a non-circular cross-section. A frame supports the seat and the table and includes a seat support. The seat support has a non-uniform cross-section including a lower section having a substantially circular cross-section and an upper section having a non-circular cross section inserting into the cavity of the seat. A caster or glide element mounts to a bottom end of the lower section of the seat support.

1. Field of the Invention
The present invention relates to a table and seating apparatus with stool type seats having seat supports that have a non-uniform cross section.
2. Description of the Prior Art
In large, multi-purpose rooms that are utilized at various times as dining rooms, meeting halls, dance areas, training rooms, classrooms and other varied activities, it is often desirable that mobile multi-purpose furniture be used. Such furniture includes tables, chairs, benches and/or stools or table and seat combinations. Table and seating combinations often utilize stool type seats that provide great utility and access for those using the table and seating system. Many table and seating structures are mounted on wheels or casters for easy transport. The units may also be foldable for easy storage.
A challenge for such systems and especially such systems that are utilized in schools is resistance to abuse by users, especially when used by teenaged children. The stool type seats for these systems are typically a lightweight molded plastic that mount to a vertical tubular support post. Although such seats are generally lightweight and provide high strength and are adequate for supporting users, such seats may be open to abuse by the users. Such seats are typically bolted to the seat support with a horizontally extending bolt. Through abuse, the bolt may be dislodged, sheared or break through the plastic lower section of the seat. If this occurs and the bolt does not retain the seat, students or other users may further abuse the seat by twisting. Where the top edge of the tubular support post is round, such twisting may act as a bore and may eventually break through the upper surface of the seat, thereby ruining the seat.
To provide a seat that cannot rotate, a seating system has been developed that has a square seat support and a seat having a corresponding square portion engaging the square seat support. Such a system was developed by Sico Incorporated over 30 years ago. Another system is also shown in U.S. Pat. No. D595,969 and U.S. Pat. No. 7,758,113.
Although such a system prevents rotation and damage caused by a circular top and of a seat support boring through a plastic seat, the configuration has several drawbacks. Table and seating systems that utilize such seats often are mounted on casters. Conventional casters use an upwardly extending round pin to mount into the lower end of a round tubular frame member. To mount the caster with a round pin into the bottom of a square channel, an adapter must often be used. Alternatively, an adapter of mounting member may be welded or otherwise attached to the square tube to provide for mounting the upwardly extending mounting pin of a caster. However, if the casters are offset from the frame member, the balance of such systems, especially folding systems, may be adversely affected and cause problems for folding and/or unfolding.
It can be seen then that a new system is needed that provides a sturdy and reliable seat that prevents abuses and damage due to rotation of the seats on a round support. Moreover, such a system should overcome the drawbacks associated with using square tubular members as a frame and mounting of casters. The present invention addresses these as well as other problems associated with table and seating systems and their seats and seat supports.


A remote alarm for use with a wearable defibrillator. The remote alarm may be a wearable remote device including a strap for disposing the wearable remote device on a wrist of a patient and communications circuitry disposed in the wearable remote device to wirelessly communicate with the wearable defibrillator. The wearable remote device may be configured to receive alarms, voice messages and prompts issued by the wearable defibrillator and to repeat those alarms, voice messages and prompts in a manner that can more easily be perceived by a patient wearing the wearable defibrillator or a bystander. The wearable remote device may further be configured to take certain actions depending upon the content of the communication, such as sending a telephone message to alert emergency personnel to the identity, location and medical condition of the patient, or sending an email to a friend, caregiver, or relative.

1. Field of the Invention
The present invention is directed to a remote alarm for use with a wearable medical device.
2. Discussion of Related Art
During the course of use, a wearable medical device, such as a wearable defibrillator, a wearable insulin pump, etc., may issue audible alarms, voice prompts or messages, or visual messages to alert the patient or a bystander to a medical condition, to direct them to take some action to correct a problem, to call for assistance, to request information from the patient or the bystander, or to provide feedback to the device so that the device may continue to function properly. For example, where the wearable medical device is a wearable defibrillator, if the device determines that the patient is experiencing cardiac arrhythmia, the device may issue alarms and voice messages instructing the patient to indicate that they are conscious by pressing and holding a button associated with the device, thereby instructing the device to withhold the delivery of a defibrillating shock. If the patient does not respond, the device may presume that the patient is unconscious, and proceed with the treatment sequence, culminating in the delivery of one or more defibrillating shocks to the body of the patient. Alarms and messages may also be directed to a bystander instructing the bystander to call for medical assistance, or to alert any bystanders that a defibrillating shock is about to be delivered and to stand clear of the patient.


The present invention provides methods, compositions, and systems for distributing molecules and complexes into reaction sites. In particular, the methods, compositions, and systems of the present invention result in an active loading of molecules and complexes into reaction sites with improved efficiency over loading by passive diffusion methods alone.

Techniques in molecular biology and molecular medicine often rely on analysis of single biological molecules. Such techniques include DNA and RNA sequencing, polymorphism detection, the detection of proteins of interest, the detection of protein-nucleic acid complexes, and many others. The high sensitivity, high throughput and low reagent costs involved in single molecule analysis make this type of analysis an increasingly attractive approach for a variety of detection and analysis problems in molecular medicine, from low cost genomics to high sensitivity marker analysis.
The small observation volumes often used for single molecule analysis methods are typically provided by immobilizing or otherwise localizing molecules of interest within an optical confinement reaction/observation region, such as an array of extremely small wells as in an array of Zero Mode Waveguides (ZMWs), and delivering molecules of interest (including for example, a template, primers, enzymes etc.,) to the reaction region. One difficulty in performing single molecule analyses occurs in loading the reaction/observation region of single molecule analysis devices with the molecules of interest (e.g., template or other analyte and/or enzyme). Entropic barriers to loading can be significant when attempting to load large reactant molecules into these nanoscale reaction sites.
While passive distribution methods are effective in ensuring that, in most cases, not more than a single template or enzyme (or other analyte) molecule is loaded in each observation/reaction volume in an array such as a ZMW array, it would be desirable to develop methods and compositions for increasing the efficiency and density of loading in such reaction sites. The present invention provides these and other features that will be apparent upon complete review of the following.

Methods and compositions for delivery of molecules and complexes to reaction sites