U.S. patent application number 13/738838 was filed with the patent office on 2013-05-23 for polymer composite material with biocide functionality.
This patent application is currently assigned to BAYER INNOVATION GMBH. The applicant listed for this patent is BAYER INNOVATION GMBH. Invention is credited to Rolf Christian BECKER, Ralf DUJARDIN, Arno SCHMUCK, Almuth STREITENBERGER, Marco TOAPANTA.
Application Number | 20130130911 13/738838 |
Document ID | / |
Family ID | 39720087 |
Filed Date | 2013-05-23 |
United States Patent
Application |
20130130911 |
Kind Code |
A1 |
DUJARDIN; Ralf ; et
al. |
May 23, 2013 |
POLYMER COMPOSITE MATERIAL WITH BIOCIDE FUNCTIONALITY
Abstract
Polymer composite material with biocide functionality,
preferably for the use in agriculture, comprising at least one base
polymer compound and at least one biocide active ingredient,
wherein the biocide active ingredient is an organic biocide that
can be emitted from the polymer composite material by diffusion
and/or osmosis and method of its production.
Inventors: |
DUJARDIN; Ralf;
(Duesseldorf, DE) ; BECKER; Rolf Christian;
(Burscheid, DE) ; TOAPANTA; Marco; (Kansas City,
KS) ; SCHMUCK; Arno; (Leichlingen, DE) ;
STREITENBERGER; Almuth; (Koeln, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BAYER INNOVATION GMBH; |
Duesseldorf |
|
DE |
|
|
Assignee: |
BAYER INNOVATION GMBH
Duesseldorf
DE
|
Family ID: |
39720087 |
Appl. No.: |
13/738838 |
Filed: |
January 10, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12176070 |
Jul 18, 2008 |
8372418 |
|
|
13738838 |
|
|
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60951016 |
Jul 20, 2007 |
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Current U.S.
Class: |
504/361 ;
427/331 |
Current CPC
Class: |
A01N 25/34 20130101;
A01N 25/10 20130101; A01G 13/0275 20130101; A01N 25/10 20130101;
A01N 33/22 20130101; A01N 43/12 20130101; A01N 43/80 20130101; A01N
47/36 20130101; A01N 57/20 20130101; A01N 25/34 20130101; A01N
33/22 20130101; A01N 43/12 20130101; A01N 43/80 20130101; A01N
47/36 20130101; A01N 57/20 20130101 |
Class at
Publication: |
504/361 ;
427/331 |
International
Class: |
A01N 25/10 20060101
A01N025/10 |
Claims
1. Polymer composite material with biocide functionality comprising
at least one base polymer compound and at least one biocide active
ingredient, wherein the biocide active ingredient comprises an
organic biocide that can be emitted from the polymer composite
material by diffusion and/or osmosis.
2. Polymer composite material according to claim 1, wherein the
biocide active ingredient is incorporated in the polymer composite
material as a molecular dispersion.
3. Polymer composite material according to claim 1, wherein the
polymer composite material comprises at least one base polymer
compound with at least one coating layer and wherein the at least
one coating layer comprises at least one biocide active
ingredient.
4. Polymer composite material according to claim 3, wherein the at
least one base polymer compound comprises different coating layers,
wherein some layers comprise the same biocide active ingredient or
different biocide active ingredients.
5. Polymer composite material according to claim 1, wherein the
organic biocide is at least one selected from the group consisting
of pesticides, herbicides, insecticides, algicides, fungicides,
moluscicides, miticides, rodenticides, germicides, antibiotics,
antibacterials, antivirals, antifungals, antiseptics,
antiprotozoals, antiparasites, antiseptics, and disinfectants.
6. Polymer composite material according to claim 3, wherein the
coating layer has a water uptake of at least 100% over a coating
layer area.
7. Polymer composite material according to claim 3, wherein the at
least one coating layer comprises at least one binder.
8. Polymer composite material according to claim 3, wherein said at
least one coating layer comprises gelatin.
9. Polymer composite material according to claim 3, wherein said at
least one coating layer comprises at least one additive.
10. Polymer composite material according to claim 3, wherein the at
least one coating layer comprises at least one carrier fluid.
11. A method for the production of a polymer composite material
comprising mixing at least one base polymer compound and at least
one biocide active ingredient so that the biocide active ingredient
is incorporated in a form of a molecular dispersion, forming the
polymer composite material in desired shape by molding and/or by
film formation.
12. Method for the production of a polymer composite material
comprising mixing at least one coating compound and at least one
biocide active ingredient so that the biocide active ingredient is
incorporated, in a form of a molecular dispersion, and to form a
first product, coating a base polymer compound with the first
product and curing the first product to form a coating layer on
said base polymer.
13. A Method according to claim 12 wherein the method further
comprises coating the base polymer compound on at least two sides
thereof, and wherein the at least one biocide active ingredient is
different on each side of said base polymer compound and/or the at
least one coating compound is different on each side of said base
polymer.
14. A method according to claim 11, adapted for use in agriculture
and/or horticulture.
15. A method as claimed in claim 14, wherein said use in
agriculture and/or horticulture comprises use as mulch film,
fumigation film, propagation film, propagation pots, nursery trays
and/or harvest trays.
16. Mulch film, fumigation film, propagation film, propagation
pots, nursery trays and/or harvest trays comprising a polymer
composite material according to claim 1.
17. A material of claim 7, wherein said binder is cross-linkable,
and after said binder is cross-linked, said binder is water
absorbing and/or gel forming.
18. A material of claim 9, wherein said additive comprises a
hardener.
19. A material of claim 10, wherein said fluid comprises water
and/or an organic solvent.
20. A material of claim 4, wherein said at least one coating layer
comprises water.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of U.S. application Ser.
No. 12/176,070, filed on Jul. 18, 2008, which claims priority to
U.S. Application No. 60/951,016, filed on Jul. 20, 2007, the
contents of each of which are incorporated herein by reference in
their entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to polymer composite materials
with biocide functionality, methods for producing such polymer
composite materials and their use, in particular for
agriculture.
[0004] 2. Description of Related Art
[0005] A wide variety of polymer materials like biodegradable mulch
films for reducing weed growth or special biodegradable
horticulture pots are known which are used in the field of
agriculture. An emphasis in the equipment of these polymer
materials lies in the task either to stabilize the material against
environmental and chemical influences or to improve the
biodegradability of the material. Examples for agricultural films
stabilized against pesticides with an additive can be found in
Japanese application JP 631 75 072. In the European patent
application EP 0214507 there are UV stabilizers described which are
used in films for outdoor agriculture.
[0006] An example of a material capable of thermal diffusion of an
active ingredient is described in DE 28 19 515 A1. A multilayered
composite material comprises a layer which is able to increase the
temperature within the material by exothermic chemical reaction so
that a functional material can be set free. However, the disclosed
inorganic chemical substances which are needed for the exothermic
reaction are harmful to the environment as well as unsuitable for
the production, harvest or transport of food and medical
articles.
[0007] Another polymer material incorporating biocide inorganic
substances is known from DE 696 29 891 T2. There, chlorine dioxide
is provided as biocide inorganic substance to act as a disinfectant
in films for food packaging. However, the handling and controlling
of the right amount of disinfectant over a given time period is
difficult complex and costly. According to the disclosed material
it involves different layers which must include a hydrophobic layer
comprising an acid freeing substance and a neighbouring hydrophilic
layer comprising chlorinate ions.
[0008] Another approach to functionalize agricultural or
horticultural polymers lies in the incorporation of inorganic
substances like copper, copper salts and finely pulverized silver
acting as disinfectants. However, the release of the active
substance is incontrollable and often involves the degradation or
dissolving of the polymer.
[0009] All yet known polymer materials in agriculture or
horticulture share the problem that the lifespan of the
functionalized material is short. Moreover, the function often only
lies in the protection of the polymer itself. However, a function
for the agricultural goods like that of a biocide is not given in a
convenient way because of the limitation to only inorganic
substances, again involving degradable or soluble polymers to set
free the inorganic substance. Like that, a lifespan required for a
growing season of 12 months or in case of reuse of several years
and/or over several planting and harvesting seasons of the
functionalized polymer material is impossible. The mechanical
properties decrease over time with increasing biodegradation
causing a molecular weight reduction of the polymer. Molecular
weight reduction reducing desired polymer performance like strength
necessary for mitigation of weather fluctuations by agricultural
films or protecting the roots of seedlings by nursery pots and
trays, for example.
SUMMARY OF THE INVENTION
[0010] Therefore, it is the object of the present invention to
provide a polymer composite material, preferably for the use in
agriculture and horticulture, which can have a variety of biocide
functionalities and which has a long lifespan.
[0011] It is another object of the present invention to provide a
method for the production of such a polymer composite material.
[0012] This object is solved by a polymer composite material with
biocide functionality, preferably for the use in agriculture,
comprising at least one base polymer compound and at least one
biocide active ingredient, wherein the biocide active ingredient is
an organic biocide that can be emitted from the polymer composite
material by diffusion and/or osmosis.
DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
[0013] Under the term base polymer compound all polymer compounds
are understood which show a sufficient UV and weather stability to
withstand constant outdoor exposure at least for 12 months and do
not react with the organic biocide active ingredient and whose
properties are not changed by the organic biocide. As the
flexibility of polymer material is dependent upon the material
thickness, flexible films as well as inflexible molded articles are
understood under the term base polymer material.
[0014] Under the term biocide active ingredient there are all
chemical substances understood which are capable of killing
different forms of living organisms and/or viruses used in fields
such as medicine, agriculture, and forestry.
[0015] In a preferred embodiment of the present invention the
biocide active ingredient or a combination of biocide active
ingredients is incorporated in the polymer composite material in
form of a molecular dispersion. Like that, an even and defined
distribution in the composite material is achieved.
[0016] In another preferred embodiment of the present invention the
biocide active ingredient is incorporated into a coating layer.
[0017] By that means the emission of the biocide active ingredient
by diffusion and/or osmosis can be facilitated and/or timed.
[0018] Coating materials are preferably applied in a thin film
(thickness of the dry coating layer preferably below 0.5 mm) to the
base polymer compounds. In order to achieve the desired
characteristics from the thin film, the coating material
formulation and the coating layer structure can be tailored in
relation to the desired part characteristics, e.g. flexible films
or rigid molded parts to facilitate and/or time the emission of the
biocide active ingredient. Coating materials can be formulated from
a wide variety of chemicals and materials or a combination of
different chemicals and applied as single layer or stacked
multilayer. Coating materials of the present invention are
preferably formulated from four components: binders, additives,
biocide active ingredients and the carrier fluid.
[0019] Binders primarily function as an adhesive to the base
polymer. Binders are polymer adhesive[k1] systems with varying
molecular weights. The molecules in the binder can be crosslinked
during the curing stage to improve strength and create the polymer
composite material.
[0020] In the preferred embodiment of the present invention the
coating material can be based on water soluble polymer adhesive
systems comprising binders which are cross-linkable[k2] and which
are after cross-linking water insoluble but water-swellable and
capable of gel-forming by water absorbing. The term
"cross-linkable" according to the present invention indicates that
the binders can form a network structure preferably initiated by
heat, pressure, radiation and/or chemicals (hereinfafter also
referred to as hardener). The term "gel-forming" according to the
present invention refers to a colloid structure comprising at least
50%, at least 75% and typically at least 95% wt liquid, which is
immobilized by surface tension between it and a macromolecular
network of fibres built from a small amount of binders. In a
preferred embodiment the liquid of the gel is water and the gel is
a hydrogel in which water is the dispersion medium.
[0021] The binders are preferably selected from the group
comprising gelatin; alginates; cellulose based polymers such as
methyl cellulose, hydroxymethyl cellulose, carboxymethylcellulose,
cellulose acetate phthalate, and the like; starch based polymers
such as carboxymethyl starch; natural gums, such as gum arabic,
locust bean gum, carrageenan gum and xanthan gum; pectins; polymers
formed from acid-group containing monomers, such as poly(acrylates)
(including poly(acrylic acid), poly(methacrylic acid), and the
like), poly(ethers), poly(acrylamides), poly(vinyl alcohol), maleic
anhydride copolymers, poly(vinyl sulfonates), hydrolyzed
acrylonitrile grafted starch, acrylic acid grafted starch,
poly(N-vinyl pyrrolidone), poly (2-hydroxyethylacrylate),
poly(2-hydroxyethyl-methacrylate), poly (sodium acrylate-co-acrylic
acid), poly(vinylsulfonic acid), poly (ethyleneoxide), block
co-polymers of ethylene oxide with polyamides, polyesters, and
polyurethanes, and salt forms mixtures and copolymers of the
above.
[0022] Particularly preferred binders comprise water soluble (but
after crosslinking insoluble) chemical and/or physical
cross-linkable adhesive polymers such as polyvinyl alcohol,
polyvinyl methyl ether; polyvinyl pyrrolidone; polyethylene oxide;
cellulose derivatives such as dextrans and starches; polyacrylates
such as polyacrylacid, polyacrylamides, methyl cellulose, carboxy
methyl cellulose, starch-based polymers, gelatin, casein, xanthan
hydroxyl-ethyl-cellulose hydroxylpropyl cellulose and/or
dispersions from block co-polymers of ethylene oxide with
polyurethane.
[0023] Illustrative examples of particularly useful gel-forming,
water absorbing cross-linkable coating binders that are capable,
under the most favorable conditions, of absorbing at least about 5,
more preferably at least 10, even more preferably at least 15 and
most preferably at least 25 times its weight in an aqueous solution
containing 0.9 weight percent sodium chloride are preferably
selected from the group comprising superabsorbers such as
poly(acrylates) including poly(acrylic acid), poly(methacrylic
acid), and the like), maleic anhydride copolymers, poly(vinyl
sulfonates), poly (sodium acrylate-co-acrylic acid),
poly(vinylsulfonic acid), (as for example described in the U.S.
Pat. Nos. 6,737,491, 6,849,685, 6,887,961, 7,115,321, 6,964,803,
6,808,801, 7,205,259), gelatin and/or dispersions from block
co-polymers of ethylene oxide with polyurethane.
[0024] A particularly useful coating material according to the
present invention comprises the combination of at least two water
absorbent cross-linkable polymer binders, wherein one water
absorbent cross-linkable polymer binder is gelatin. In a
particularly preferred embodiment coating layers comprise the
combination of a gelatin binder and a superabsorber binder such as
a poly(acrylates) binder.
[0025] Gelatin has been shown to be surprisingly beneficial as it
supports the attachment of the water absorbent cross-linkable
polymers to the base polymer without substantially interfering with
the properties of the water absorbent cross-linkable polymers.
[0026] Any gelatin such as photographic gelatin, feed gelatin,
edible gelatin, industrial gelatin, protein gelatin can be used for
such a preferred coating layer. By adding as an additive a
hardener, the gelatin is cross-linked due to a reaction of free
amino-, imino- and hydroxyl groups.
[0027] Additives are defined as insoluble pigments or low molecular
weight chemicals in coating formulations that allow coatings to
perform specific functions but do not contribute to the biocide
function. Additives include but are not limited to pigments.
Pigments are typically the colorant portion of a coating material,
but can also perform corrosion protection or stability in
ultraviolet (UV) light. Additives also include but are not limited
to non-pigments. Non-pigment additives include stabilizers to block
attacks of ultraviolet light or heat, hardener to speed up the
cross-linking reaction, co-solvents to increase viscosity, or
plasticizers to improve uniform coating.
[0028] In a further preferred embodiment of the invention, a
hardener, preferably formaldehyde is used as an additive to
crosslink the coating layer material and to improve the attachment
of the layer material to the base polymer.
[0029] A particularly useful composite material relates to a base
polymer wherein the coating materials comprise a combination of
water absorbent cross-linkable polymers, preferably superabsorbers,
more preferably polyacrylates, gelatin and a hardener, preferably
formaldehyde.
[0030] The carrier fluid is typically a liquid such as an organic
solvent or water. The carrier fluid allows the coating materials to
flow and be applied by methods such as spraying, dipping, cascade
and/or curtain casting.[k3] This component may be in the coating
formulation before application, but evaporates afterwards to allow
the solid materials to immobilize and form the coating layer. The
resulting polymer composite material can optionally be dried.
[0031] The carrier fluid might therefore be completely absent,
partially present or present in the final, ready-to-use polymer
composite material. In a preferred embodiment the carrier fluid is
absent or only partially present in the final, ready-to-use polymer
composite material. However, the skilled person in the art
acknowledges that water or another liquid will be absorbed by the
polymer composite material during use and will play an important
role for the functionality of the polymer composite material.
[0032] In a further preferred embodiment of the invention the
organic solvent is, ethanol, aceton, 1,4-dioxane, tetrahydrofuran,
dichlormethane, acetonitrile, dimethylformamide, dimethylsulfoxide,
acetic acid, n-butanol, isopropanol, n-propanol, methanol, formic
acid, other solvents known to the skilled person in the art and/or
aqueous solutions thereof.
[0033] Coating materials of the present invention comprise at least
one biocide active ingredient (hereinafter also referred to as a
biocide).
[0034] Coating formulations vary widely, with different types and
amounts of binders, additives, carrier fluids and biocide active
ingredients. The differences in coating formulations provide film
characteristics specifically set for the part and its end-use.
Often, one type of coating material cannot be formulated to provide
all of the desired properties. Several layers of different coating
materials may be applied to a base polymer to form the coating
film.
[0035] The polymer composite material according to another
preferred embodiment of the present invention can be a multilayered
coating structure and the biocide active ingredient is incorporated
into repeating or one coating layers.
[0036] By the incorporation of the biocide active ingredient into
repeating coating layers a control of diffusion and/or osmosis
rates is even better achievable. Apart from that, different biocide
active ingredients can be incorporated in different layers. The
present invention, however, also relates to an embodiment wherein a
mixture of at least two biocide active ingredients are incorporated
into one coating layer. Depending on the plant growth and the
possible seasonally changing requirements in terms of pests, fungi,
and the like, a tailored approach to biocide treatment can be
provided.
[0037] In a preferred embodiment of the invention, the at least one
biocide active ingredient can be incorporated into the same coating
layer as the binders. Preferred is an embodiment wherein the layer
with the at least one biocide comprises gelatin.
[0038] The organic biocide is preferably selected from the group
consisting of pesticides, herbicides, insecticides, algicides,
fungicides, moluscicides, miticides, and rodenticides. Moreover,
the organic biocide can even more preferably be selected from the
group consisting of germicides, antibiotics, antibacterials,
antivirals, antifungals, antiseptics, antiprotozoals, and
antiparasites.
[0039] In another preferred embodiment of the invention the organic
biocide is selected from the group of antiseptics and/or
disinfectants for medical use and food.
[0040] As the regulations for chemical substances being considered
safe for the use in the agricultural, food and medical field are
constantly changing, such organic biocide active ingredients are
most preferred for the present invention which comply with the
actual official regulations for chemical substances and especially
for antiseptics and disinfectants in those fields. Especially those
substances which are listed in the European the Biocidal Products
Directive (98/8/EC) by the European Commission are preferably used
as biocide active ingredients according to the present
invention.
[0041] In another preferred embodiment of the present invention the
organic biocide is selected from the group comprising of acetamides
and anilides herbicides, thiocarbamate herbicides, chlorphenoxy
herbicides, dipyridyl herbicides, dinitrocresolic herbicides,
cyclohexyloxim herbicides, phosphonate herbicides, traizolon
herbicides, urea herbicide derivatives and/or mixtures thereof.
[0042] Particular herbicides according to the present invention are
selected from the group comprising acetochlor, acibenzolar,
acibenzolar-s-methyl, acifluorfen, acifluorfen-sodium, aclonifen,
alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn,
amicarbazone, amidochlor, amidosulfuron, aminopyralid, amitrole,
ammoniumsulfamat, ancymidol, anilofos, asulam, atrazine,
azafenidin, azimsulfuron, aziprotryn, BAH-043, BAS-140H, BAS-693H,
BAS-714H, BAS-762H, BAS-776H, BAS-800H, beflubutamid, benazolin,
benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulide,
bensulfuron-methyl, bentazone, benzfendizone, benzobicyclon,
benzofenap, benzofluor, benzoylprop, bifenox, bilanafos,
bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil,
bromobutide, bromofenoxim, bromoxynil, bromuron, buminafos,
busoxinone, butachlor, butafenacil, butamifos, butenachlor,
butralin, butroxydim, butylate, cafenstrole, carbetamide,
carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chloramben,
chlorazifop, chlorazifop-butyl, chlorbromuron, chlorbufam,
chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol,
chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl,
chlormequat-chlorid, chlornitrofen, chlorophthalim,
chlorthal-dimethyl, chlorotoluron, chlorsulfuron, cinidon,
cinidon-ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop
clodinafop-propargyl, clofencet, clomazone, clomeprop, cloprop,
clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide,
cyanazine, cyclanilide, cycloate, cyclosulfamuron, cycloxydim,
cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyprazine,
cyprazole, 2,4-D, 2,4-DB, daimuron/dymron, dalapon, daminozide,
dazomet, n-decanol, desmedipham, desmetryn, detosyl-pyrazolate
(DTP), diallate, dicamba, dichlobenil, dichlorprop, dichlorprop-p,
diclofop, diclofop-methyl, diclofop-p-methyl, diclosulam,
diethatyl, diethatyl-ethyl, difenoxuron, difenzoquat, diflufenican,
diflufenzopyr, diflufenzopyr-sodium, dimefuron, dikegulac-sodium,
dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid,
dimethenamid-p, dimethipin, dimetrasulfuron, dinitramine, dinoseb,
dinoterb, diphenamid, dipropetryn, diquat, diquat-dibromide,
dithiopyr, diuron, DNOC, eglinazine-ethyl, endothal, eptc,
esprocarb, ethalfluralin, ethametsulfuron-methyl, ethephon,
ethidimuron, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl,
ethoxysulfuron, etobenzanid, F-5331, i.e.
N-[2-chlor-4-fluor-5-[4-(3-fluorpropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-y-
l]-phenyl]-ethansulfonamid, fenoprop, fenoxaprop, fenoxaprop-p,
fenoxaprop-ethyl, fenoxaprop-p-ethyl, fentrazamide, fenuron,
flamprop, flamprop-m-isopropyl, flamprop-m-methyl, flazasulfuron,
florasulam, fluazifop, fluazifop-p, fluazifop-butyl,
fluazifop-p-butyl, fluazolate, flucarbazone, flucarbazone-sodium,
flucetosulfuron, fluchloralin, flufenacet (thiafluamide),
flufenpyr, flufenpyr-ethyl, flumetralin, flumetsulam, flumiclorac,
flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron,
fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, flupoxam,
flupropacil, flupropanate, flupyrsulfuron,
flupyrsulfuron-methyl-sodium, flurenol, flurenol-butyl, fluridone,
fluorochloridone, fluoroxypyr, fluoroxypyr-meptyl, flurprimidol,
flurtamone, fluthiacet, fluthiacet-methyl, fluthiamide, fomesafen,
foramsulfuron, forchlorfenuron, fosamine, furyloxyfen,
gibberellinic acid, glufosinate, 1-glufosinate,
1-glufosinate-ammonium, glufosinate-ammonium, glyphosate,
glyphosate-isopropylammonium, H-9201, halosafen, halosulfuron,
halosulfuron-methyl, haloxyfop, haloxyfop-p, haloxyfop-ethoxyethyl,
haloxyfop-p-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl,
hexazinone, hnpc-9908, HOK-201, HW-02, imazamethabenz,
imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin,
imazethapyr, imazosulfuron, inabenfide, indanofan, indolacetic acid
(IAA), 4-indol-3-yl-butanoic acid (IBA), iodosulfuron,
iodosulfuron-methyl-sodium, ioxynil, isocarbamid, isopropalin,
isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole,
isoxapyrifop, IDH-100, KUH-043, KUH-071, karbutilate, ketospiradox,
lactofen, lenacil, linuron, maleinic acid hydrazid, MCPA, MCPB,
MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium,
mecoprop-butotyl, mecoprop-p-butotyl, mecoprop-p-dimethylammonium,
mecoprop-p-2-ethylhexyl, mecoprop-p-kalium, mefenacet, mefluidide,
mepiquat-chlorid, mesosulfuron, mesosulfuron-methyl, mesotrione,
methabenzthiazuron, metam, metamifop, metamitron, metazachlor,
methazole, methoxyphenone, methyldymron, 1-methylcyclopropen,
methylisothiocyanat, metobenzuron, metobenzuron, metobromuron,
metolachlor, s-metolachlor, metosulam, metoxuron, metribuzin,
metsulfuron, metsulfuron-methyl, molinate, monalide, monocarbamide,
monocarbamide-dihydrogensulfat, monolinuron, monosulfuron, monuron,
MT 128, MT-5950, i.e.
N-[3-chlor-4-(1-methylethyl)-phenyl]-2-methylpentanamide, NGGC-011,
naproanilide, napropamide, naptalam, NC-310, i.e.
4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, neburon,
nicosulfuron, nipyraclofen, nitralin, nitrofen,
nitrophenolat-sodium (mixture of isomers), nitrofluorfen, nonanoic
acid, norflurazon, orbencarb, orthosulfamuron, oryzalin,
oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen,
paclobutrazol, paraquat, paraquat-dichlorid, pelargonic acid
(nonanoic acid), pendimethalin, pendralin, penoxsulam,
pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham,
phenmedipham, phenmedipham-ethyl, picloram, picolinafen, pinoxaden,
piperophos, pirifenop, pirifenop-butyl, pretilachlor,
primisulfuron, primisulfuron-methyl, probenazole, profluazol,
procyazine, prodiamine, prifluraline, profoxydim, prohexadione,
prohexadione-calcium, prohydrojasmone, prometon, prometryn,
propachlor, propanil, propaquizafop, propazine, propham,
propisochlor, propoxycarbazone, propoxycarbazone-sodium,
propyzamide, prosulfalin, prosulfocarb, prosulfuron, prynachlor,
pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole,
pyrazolynate (pyrazolate), pyrazosulfuron-ethyl, pyrazoxyfen,
pyribambenz, pyribambenz-isopropyl, pyribenzoxim, pyributicarb,
pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl,
pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone,
pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop,
quizalofop-ethyl, quizalofop-p, quizalofop-p-ethyl,
quizalofop-p-tefuryl, rimsulfuron, secbumeton, sethoxydim, siduron,
simazine, simetryn, SN-106279, sulcotrione, sulfallate (cdec),
sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate
(glyphosate-trimesium), sulfosulfuron, SYN-523, SYP-249, SYP-298,
SYP-300, tebutam, tebuthiuron, tecnazene, tefuryltrione,
tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor,
terbumeton, terbuthylazine, terbutryn, th-547, thenylchlor,
thiafluamide, thiazafluoron, thiazopyr, thidiazimin, thidiazuron,
thiencarbazone, thiencarbazone-methyl, thifensulfuron,
thifensulfuron-methyl, thiobencarb, tiocarbazil, topramezone,
tralkoxydim, triallate, triasulfuron, triaziflam, triazofenamide,
tribenuron, tribenuron-methyl, trichlor acetic acid (tca),
triclopyr, tridiphane, trietazine, trifloxysulfuron,
trifloxysulfuron-sodium, trifluralin, triflusulfuron,
triflusulfuron-methyl, trimeturon, trinexapac, trinexapac-ethyl,
tritosulfuron, tsitodef, uniconazole, uniconazole-p, vernolate,
ZJ-0166, ZJ-0270, ZJ-0543, ZJ-0862, as well as the following
compounds
##STR00001##
[0043] In another preferred embodiment of the present invention the
organic biocide is selected from the group comprising antibiotics
insecticides cyclodien insecticides, insect growth regulators,
carbamate insecticides, nicotenoide insecticides, pyrethroid
herbicides, oxadiazine insecticides, organophosphorus insecticides
and/or mixtures thereof.
[0044] The following insects may be mentioned as examples and as
preferred--but without any limitation:
[0045] Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis,
Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis,
Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus
brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis,
Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus
spec. Tryptodendron spec. Apate monachus, Bostrychus capucins,
Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus;
Hymenopterons, such as Sirex juvencus, Urocerus gigas, Urocerus
gigas taignus, Urocerus augur; Termites, such as Kalotermes
flavicollis, Cryptotermes brevis, Heterotermes indicola,
Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes
lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,
Coptotermes formosanus; Bristletails, such as Lepisma
saccharina.
[0046] Particular insecticides according to the present invention
are selected from the group comprising acetylcholinesterase (AChE)
inhibitors such as for example carbamates, e.g. alanycarb,
aldicarb, aldoxycarb, allyxycarb, aminocarb, bendiocarb,
benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim,
carbaryl, carbofuran, carbosulfan, cloethocarb, dimetilan,
ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb,
isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl,
pirimicarb, promecarb, propoxur, thiodicarb, thiofanox,
trimethacarb, XMC, and xylylcarb; or organophosphates, e.g.
acephate, azamethiphos, azinphos (-methyl, -ethyl),
bromophos-ethyl, bromfenvinfos (-methyl), butathiofos, cadusafos,
carbophenothion, chlorethoxyfos, chlorfenvinphos, chlormephos,
chlorpyrifos (-methyl/-ethyl), coumaphos, cyanofenphos, cyanophos,
chlorfenvinphos, demeton-S-methyl, demeton-S-methylsulphon,
dialifos, diazinon, dichlofenthion, dichlorvos/DDVP, dicrotophos,
dimethoate, dimethylvinphos, dioxabenzofos, disulfoton, EPN,
ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion,
fensulfothion, fenthion, flupyrazofos, fonofos, formothion,
fosmethilan, fosthiazate, heptenophos, iodofenphos, iprobenfos,
isazofos, isofenphos, isopropyl, O-salicylate, isoxathion,
malathion, mecarbam, methacrifos, methamidophos, methidathion,
mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl,
parathion (-methyl/-ethyl), phenthoate, phorate, phosalone,
phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos
(-methyl/ethyl), profenofos, propaphos, propetamphos, prothiofos,
prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos,
sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos,
tetrachlorvinphos, thiometon, triazophos, triclorfon, vamidothion,
and imicyafos. GABA-gated chloride channel antagonists such as for
example organochlorines, e.g. camphechlor, chlordane, endosulfan,
gamma-HCH, HCH, heptachlor, lindane, and methoxychlor; or fiproles
(phenylpyrazoles), e.g. acetoprole, ethiprole, fipronil,
pyrafluprole, pyriprole, and vaniliprole. Sodium channel
modulators/voltage-dependent sodium channel blockers, such as for
example pyrethroids, e.g. acrinathrin, allethrin (d-cis-trans,
d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin
S-cyclopentyl isomer, bioethanomethrin, biopermethrin,
bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin,
cis-permethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin,
cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin,
deltamethrin, empenthrin (1R isomer), esfenvalerate, etofenprox,
fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate,
flubrocythrinate, flucythrinate, flufenprox, flumethrin,
fluvalinate, fubfenprox, gamma-cyhalothrin, imiprothrin, kadethrin,
lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-),
phenothrin (1R trans isomer), prallethrin, profluthrin,
protrifenbute, pyresmethrin, resmethrin, RU 15525, silafluofen,
tau-fluvalinate, tefluthrin, terallethrin, tetramethrin
(-1R-isomer), tralomethrin, transfluthrin, ZXI 8901, pyrethrin
(pyrethrum), eflusilanat; DDT; or methoxychlor. Nicotinergic
acetylcholine receptor agonists/antagonists such as for example
chloronicotinyls, e.g. acetamiprid, clothianidin, dinotefuran,
imidacloprid, imidaclothiz, nitenpyram, nithiazine, thiacloprid,
thiamethoxam, AKD-1022, nicotine, bensultap, cartap,
thiosultap-sodium, and thiocylam. Allosteric acetylcholine receptor
modulators (agonists) such as for example spinosyns, e.g. spinosad
and spinetoram. Chloride channel activators, such as for example
mectins/macrolides, e.g. abamectin, emamectin, emamectin benzoate,
ivermectin, lepimectin, and milbemectin; or juvenile hormone
analogues, e.g. hydroprene, kinoprene, methoprene, epofenonane,
triprene, fenoxycarb, pyriproxifen, and diofenolan.
[0047] Active ingredients with unknown or non-specific mechanisms
of action such as for example gassing agents, e.g. methyl bromide,
chloropicrin and sulfuryl fluoride; selective antifeedants, e.g.
cryolite, pymetrozine, pyrifluquinazon and flonicamid; or mite
growth inhibitors, e.g. clofentezine, hexythiazox, etoxazole.
Oxidative phosphorylation inhibitors, ATP disruptors such as for
example diafenthiuron; organotin compounds, e.g. azocyclotin,
cyhexatin and fenbutatin oxide; or propargite, tetradifon.
Oxidative phoshorylation decouplers acting by interrupting the H
proton gradient such as for example chlorfenapyr, binapacryl,
dinobuton, dinocap and DNOC. Microbial disruptors of the insect gut
membrane such as for example Bacillus thuringiensis strains. Chitin
biosynthesis inhibitors such as for example benzoylureas, e.g.
bistrifluoron, chlorfluazuron, diflubenzuron, fluazuron,
flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,
noviflumuron, penfluoron, teflubenzuron or triflumuron. Buprofezin.
Moulting disruptors such as for example cyromazine. Ecdysone
agonists/disruptors such as for example diacylhydrazines, e.g.
chromafenozide, halofenozide, methoxyfenozide, tebufenozide, and
JS-118; or azadirachtin. Octopaminergic agonists such as for
example amitraz. Site III electron transport inhibitors/site II
electron transport inhibitors such as for example hydramethylnon;
acequinocyl; fluacrypyrim; or cyflumetofen and cyenopyrafen.
Electron transport inhibitors such as for example Site I electron
transport inhibitors, from the group of the METI acaricides, e.g.
fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad,
tolfenpyrad, and rotenone; or voltage-dependent sodium channel
blockers, e.g. indoxacarb and metaflumizone. Fatty acid
biosynthesis inhibitors such as for example tetronic acid
derivatives, e.g. spirodiclofen and spiromesifen; or tetramic acid
derivatives, e.g. spirotetramat. Neuronal inhibitors with unknown
mechanism of action, e.g. bifenazate. Ryanodine receptor effectors
such as for example diamides, e.g. flubendiamide,
(R),(S)-3-chloro-N-1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)-
ethyl]phenyl}-N2-(1-methyl-2-methylsulphonylethyl)phthalamide,
chlorantraniliprole (Rynaxypyr), or Cyazypyr. Further active
ingredients with unknown mechanism of action such as for example
amidoflumet, benclothiaz, benzoximate, bromopropylate, buprofezin,
chinomethionat, chlordimeform, chlorobenzilate, clothiazoben,
cycloprene, dicofol, dicyclanil, fenoxacrim, fentrifanil,
flubenzimine, flufenerim, flutenzin, gossyplure, japonilure,
metoxadiazone, petroleum, potassium oleate, pyridalyl, sulfluramid,
tetrasul, triarathene or verbutine; or one of the following known
active compounds
[0048]
4-{[(6-brompyrid-3-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on
(known from WO 2007/115644),
4-{[(6-fluorpyrid-3-yl)methyl](2,2-difluorethyl)amino}furan-2(5H)-on
(known from WO 2007/115644),
4-{[(2-chlor-1,3-thiazol-5-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on
(known from WO 2007/115644),
4-{[(6-chlorpyrid-3-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on
(known from WO 2007/115644),
4-{[(6-chlorpyrid-3-yl)methyl](2,2-difluorethyl)amino}furan-2(5H)-on
known from WO 2007/115644),
4-{[(6-chlor-5-fluorpyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on
(known from WO 2007/115643),
4-{[(5,6-dichlorpyrid-3-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on
(known from WO 2007/115646),
4-{[(6-chlor-5-fluorpyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on
(known from WO 2007/115643),
4-{[(6-chlorpyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on
(known from EP-A-0 539 588),
4-{[(6-chlorpyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (known
from EP-A-0 539 588),
[(6-chlorpyridin-3-yl)methyl](methyl)oxido-.lamda.4-sulfanylidencyanamid
(known from WO 2007/149134),
[1-(6-chlorpyridin-3-yl)ethyl](methyl)oxido-.lamda.4-sulfanylidencyanamid
(known from WO 2007/149134) and its diastereomeres (A) and (B)
##STR00002##
[0049] (also known from WO 2007/149134),
[(6-trifluormethylpyridin-3-yl)methyl](methyl)oxido-.lamda.4-sulfanyliden-
cyanamid (known from WO 2007/095229), or
[1-(6-trifluormethylpyridin-3-yl)ethyl](methyl)oxido-.lamda.4-sulfanylide-
ncyanamid (known from WO 2007/149134) and its diastereomeres (C)
and (D)
##STR00003##
(also known from WO 2007/149134).
[0050] In another preferred embodiment of the present invention the
organic biocide is selected from the group comprising acetamide and
anilide fungicides, aliphatic nitrogen fungicides, aromatic
fungicides, thiocarbamate fungicides, oxazol fungicides,
organophosphorous fungicides, phatlimid fungicides, strobillurin
fungicides, urea derivative fungicides, quaternary ammonium
antiseptic compounds, quaternary ammonium related antiseptic
compounds like chlorhexidine gluconate, polyhexamethylene biguanide
hydrochloride, octenidine dihydrochloride and/or mixtures
thereof.
[0051] Particular fungicides according to the present invention are
selected from the group comprising inhibitors of the nucleic acid
synthesis such as for example benalaxyl, benalaxyl-M, bupirimate,
clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazol,
mefenoxam, metalaxyl, metalaxyl-M, ofurace, oxadixyl and oxolinic
acid. Inhibitors of the mitosis and cell division such as for
example benomyl, carbendazim, chlorfenazole, diethofencarb,
ethaboxam, fuberidazole, profenofos, pencycuron, thiabendazole,
thiophanate, thiophanate-methyl and zoxamide. Inhibitors of the
respiration such as for example diflumetorim as CI-respiration
inhibitor; bixafen, boscalid, carboxin, fenfuram, flutolanil,
fluopyram, furametpyr, furmecyclox, mepronil, oxycarboxin,
penthiopyrad, thifluzamide as CII-respiration inhibitor;
amisulbrom, azoxystrobin, cyazofamid, dimoxystrobin, enestrobin,
famoxadone, fenamidone, fluoxastrobin, kresoxim-methyl,
metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin,
pyribencarb, trifloxystrobin as CIII-respiration inhibitor.
Compounds capable to act as an uncoupler such as like for example
dinocap, fluazinam and meptyldinocap. Inhibitors of the ATP
production such as for example fentin acetate, fentin chloride,
fentin hydroxide, and silthiofam. Inhibitors of the amino acid
and/or protein biosynthesis such as for example andoprim,
blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride
hydrate, mepanipyrim and pyrimethanil. Inhibitors of the signal
transduction such as for example fenpiclonil, fludioxonil and
quinoxyfen. Inhibitors of the lipid and membrane synthesis such as
for example biphenyl, chlozolinate, edifenphos, etridiazole,
iodocarb, iprobenfos, iprodione, isoprothiolane, procymidone,
propamocarb, propamocarb hydrochloride, pyrazophos,
tolclofos-methyl and vinclozolin. Inhibitors of the ergosterol
biosynthesis such as for example aldimorph, azaconazole,
bitertanol, bromuconazole, cyproconazole, diclobutrazole,
difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph
acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole,
fenhexamid, fenpropidin, fenpropimorph, fluquinconazole,
flurprimidol, flusilazole, flutriafol, furconazole,
furconazole-cis, hexaconazole, imazalil, imazalil sulfate,
imibenconazole, ipconazole, metconazole, myclobutanil, naftifine,
nuarimol, oxpoconazole, paclobutrazol, pefurazoate, penconazole,
piperalin, prochloraz, propiconazole, prothioconazole,
pyributicarb, pyrifenox, quinconazole, simeconazole, spiroxamine,
tebuconazole, terbinafine, tetraconazole, triadimefon, triadimenol,
tridemorph, triflumizole, triforine, triticonazole, uniconazole,
viniconazole and voriconazole. Inhibitors of the cell wall
synthesis such as for example benthiavalicarb, dimethomorph,
flumorph, iprovalicarb, mandipropamid, polyoxins, polyoxorim,
validamycin A, and valiphenal. Inhibitors of the melanine
biosynthesis such as for example carpropamid, diclocymet,
fenoxanil, phthalide, pyroquilon and tricyclazole. Compounds
capable to induce a host defence such as like for example
acibenzolar-S-methyl probenazole, and tiadinil. Compounds capable
to have a multisite action such as like for example Bordeaux
mixture, captafol, captan, chlorothalonil, copper naphthenate,
copper oxide, copper oxychloride, copper preparations such as
copper hydroxide, copper sulphate, dichlofluanid, dithianon,
dodine, dodine free base, ferbam, fluorofolpet, folpet, guazatine,
guazatine acetate, iminoctadine, iminoctadine albesilate,
iminoctadine triacetate, mancopper, mancozeb, maneb, metiram,
metiram zinc, oxine-copper, propineb, sulphur and sulphur
preparations including calcium polysulphide, thiram, tolylfluanid,
zineb and ziram. Further compounds like for example
3-(difluoromethyl)-1-methyl-N-[(9R)-9-(1-methylethyl)-1,2,3,4-tetrahydro--
1,4-methanonaphthalen-5-yl]-1H-pyrazole-4-carboxamide,
3-(difluoromethyl)-1-methyl-N-[(9S)-9-(1-methylethyl)-1,2,3,4-tetrahydro--
1,4-methanonaphthalen-5-yl]-1H-pyrazole-4-carboxamide,
3-(difluoromethyl)-N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-1-meth-
yl-1H-pyrazole-4-carboxamide,
2-chloro-N-(4'-prop-1-yn-1-ylbiphenyl-2-yl)pyridine-3-carboxamide,
2-chloro-N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carbox-
amide,
5-fluoro-1,3-dimethyl-N-(4'-prop-1-yn-1-ylbiphenyl-2-yl)-1H-pyrazol-
e-4-carboxamide,
N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-5-fluoro-1,3-dimethyl-1H--
pyrazole-4-carboxamide,
3-(difluoromethyl)-1-methyl-N-(4'-prop-1-yn-1-ylbiphenyl-2-yl)-1H-pyrazol-
e-4-carboxamide,
3-(difluoromethyl)-N-[4'-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]--
1-methyl-1H-pyrazole-4-carboxamide,
N-(3-tert-butyl-2-ethenylphenyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-
-4-carboxamide,
1-methyl-N-[9-(1-methylethyl)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5--
yl]-3-(trifluoromethyl)-4,5-dihydro-1H-pyrazole-4-carboxamide,
N-(4'-chlorobiphenyl-2-yl)-1-methyl-3-(trifluoromethyl)-4,5-dihydro-1H-py-
razole-4-carboxamide,
N-[9-(dichloromethylidene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-
-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,
N-[4'-(3-cyano-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-3-(difluoromethyl)-1--
methyl-1H-pyrazole-4-carboxamide,
rel-3-(difluoromethyl)-1-methyl-N-[(1R,4S)-4-(1-methylethyl)-1,2,3,4-tetr-
ahydro-1,4-methanonaphthalen-5-yl]-1H-pyrazole-4-carboxamide,
N-[9-(dibromomethylidene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]--
3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,
rel-3-(difluoromethyl)-1-methyl-N-[(1R,4S)-9-methylidene-1,2,3,4-tetrahyd-
ro-1,4-methanonaphthalen-5-yl]-1H-pyrazole-4-carboxamide,
rel-3-(difluoromethyl)-1-methyl-N-[(1R,4S)-1,2,3,4-tetrahydro-1,4-methano-
naphthalen-5-yl]-1H-pyrazole-4-carboxamide,
3-(difluoromethyl)-N-[9-(difluoromethylidene)-1,2,3,4-tetrahydro-1,4-meth-
anonaphthalen-5-yl]-1-methyl-1H-pyrazole-4-carboxamide,
N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carbo-
xamide,
N-{2-[1,1'-bi(cyclopropyl)-2-yl]phenyl}-3-(difluoromethyl)-1-methy-
l-1H-pyrazole-4-carboxamide,
(2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}pheny-
l)-2-(methoxyimino)-N-methylethanamide,
2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)pyridine-3-carboxam-
ide,
N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzam-
ide,
5-methoxy-2-methyl-4-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylid-
ene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one,
(2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl-
]ethylidene}amino)oxy]methyl}phenyl)ethanamide,
(2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3-(trifluoromethyl)phenyl]e-
thoxy}imino)methyl]phenyl}ethanamide,
(2E)-2-{2-[({(1E)-1-(3-{[(E)-1-fluoro-2-phenylethenyl]oxy}phenyl)ethylide-
ne]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide,
1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol, methyl
1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)-1H-imidazole-5-carboxylate,
N-ethyl-N-methyl-N'-{2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)pr-
opoxy]phenyl}imidoformamide,
N-ethyl-N-methyl-N'-{2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)pr-
opoxy]phenyl}imidoformamide,
N'-{5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-et-
hyl-N-methylimidoformamide,
O-{1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl}1H-imidazole-1-carboth-
ioate,
N-[2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)eth-
yl]-N2-(methylsulfonyl)valinamide,
5-chloro-6-(2,4,6-trifluorophenyl)-N-[(1R)-1,2,2-trimethylpropyl][1,2,4]t-
riazolo[1,5-a]pyrimidin-7-amine,
5-chloro-N-[(1R)-1,2-dimethylpropyl]-6-(2,4,6-trifluorophenyl)[1,2,4]tria-
zolo[1,5-a]pyrimidin-7-amine,
5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triaz-
olo[1,5-a]pyrimidine, propamocarb-fosetyl,
(2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylethenyl]oxy}phenyl)ethylid-
ene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamide,
1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl
1H-imidazole-1-carboxylate,
1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1H-p-
yrazole-4-carboxamide,
2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine,
2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, 2-phenylphenol and
salts,
3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-py-
razole-4-carboxamide, 3,4,5-trichloropyridine-2,6-dicarbonitrile,
3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine,
3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine,
4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine,
quinolin-8-ol, benthiazole, bethoxazin, capsimycin, carvone,
chinomethionat, cufraneb, cyflufenamid, cymoxanil, dazomet,
debacarb, dichlorophen, diclomezine, dicloran, difenzoquat,
difenzoquat methylsulphate, diphenylamine, ecomate, ferimzone,
flumetover, fluopicolide, fluoroimide, flusulfamide,
fosetyl-aluminium, fosetyl-calcium, fosetyl-sodium,
hexachlorobenzene, irumamycin, isotianil, methasulfocarb, methyl
(2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}thio)methyl]phenyl-
}-3-methoxyacrylate, methyl isothiocyanate, metrafenone,
mildiomycin,
N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide,
N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide,
N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-1-yloxy)pheny-
l]propanamide,
N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloropyridine-3-carboxami-
de,
N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloropyridine-3-carbo-
xamide,
N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodopyridine--
3-carboxamide,
N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl-
]methyl}-2-phenylacetamide,
N-{(E)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl-
]methyl}-2-phenylacetamide, natamycin, nickel
dimethyldithiocarbamate, nitrothal-isopropyl, octhilinone,
oxamocarb, oxyfenthiin, pentachlorophenol and salts, phosphorous
acid and its salts, propamocarb fosetylate, propanosine-sodium,
proquinazid, pyrroInitrine, quintozene, S-prop-2-en-1-yl
5-amino-2-(1-methylethyl)-4-(2-methylphenyl)-3-oxo-2,3-dihydro-1H-pyrazol-
e-1-carbothioate, tecloftalam, tecnazene, triazoxide, trichlamide,
5-chloro-N'-phenyl-N'-prop-2-yn-1-ylthiophene-2-sulfonohydrazide
and zarilamid, 8-hydroxyquinoline-sulphate,
2,3-dibutyl-6-chloro-thieno[2,3-d]pyrimidin-4(3H)one, chloroneb,
prothiocarb, binapacryl, and cyprosulfamide.
[0052] Common names are used in accordance with the International
Organization for Standardization (ISO) or the chemical names, if
appropriate together with a customary code number of the compounds
and always comprise all applicable forms such as acids, salts,
ester, or modifications such as isomers, like stereoisomers and
optical isomers.
[0053] The biocide active ingredients of the present invention may
further possess asymmetric carbons, and thus encompass optical
isomers. Additionally, the biocide active ingredients which may be
used according to the invention can be present in different
polymorphic forms or as a mixture of different polymorphic forms.
Both the pure polymorphs and the polymorph mixtures are suitable
according to the invention.
[0054] The biocide active ingredient which is suitable according to
the invention may be formulated and/or applied with one or more
additional biocide active ingredient, compound or synergist. Such
combinations may provide certain advantages, such as, without
limitation, exhibiting synergistic effects for greater control of
insect pests, reducing rates of application of insecticide thereby
minimizing any impact to the environment and to worker safety,
controlling a broader spectrum of insect pests, safening of crop
plants to phytotoxicity, and improving tolerance by non-pest
species, such as mammals and fish. Additional compounds include,
without limitation, other pesticides, plant growth regulators,
fertilizers, soil conditioners, or other agricultural chemicals.
Synergists are compounds which increase the action of the biocide
active ingredient, without it being necessary for the synergistic
agent added to be active itself.
[0055] Some of the biocide active ingredients which are suitable
according to the invention act not only against plant, hygiene and
stored product pests, but also in the veterinary medicine sector
against animal parasites (ecto- and endoparasites), such as hard
ticks, soft ticks, mange mites, leaf mites, flies (biting and
licking), parasitic fly larvae, lice, hair lice, feather lice and
fleas.
[0056] Some of the biocide active ingredients which are suitable
according to the invention also have a strong insecticidal action
against insects which destroy industrial materials. Industrial
materials in the present connection are to be understood as meaning
non-living materials, such as, preferably, plastics, adhesives,
sizes, papers and cardboards, leather, wood and processed wood
products and coating compositions.
[0057] In another preferred embodiment the composite material of
the present invention comprises at least one biocide active
ingredient that is efficient against insecticidal action of insects
which destroy the base polymer.
[0058] The biocide active ingredients which are suitable according
to the invention can likewise be employed for protecting composite
materials which come into contact with seawater or brackish water,
such as hulls, screens, nets, buildings, moorings and signalling
systems, against fouling.
[0059] Furthermore, some of the biocide active ingredients which
are suitable according to the invention, alone or in combinations
with other active compounds, may be employed as antifouling
agents.
[0060] Most preferably, the biocide active ingredient of the
present invention is a non-liquid non-oil substance at room
temperature with low volatility whereby the substance can be solid
or can be formulated as a substance in solid form. The choice of
such substances improves the release controllability and the
storage stability of the polymer composite material. Especially,
essential oils as biocide active ingredients should be avoided
because of the difficulty to provide a stable dispersion in the
polymer base compound or coating layer without exudation of the
biocide. Furthermore, the mechanical stability of the polymer
composite material could be deterred in the production process due
to bubble wrap and the like if liquids or substances with high
volatility would be incorporated.
[0061] The base polymer compound according to the present invention
can be selected from the group consisting of polyethylene
terephthalate, polyvinyl chloride, polyolefins such as polyethylene
(such as for example LDPE, HDPE) and polypropylene, polystyrene,
polyester, polyether, polyacrylate, polycarbonate, polyamide and
polyurethane which can optionally comprise commonly used pigments,
UV stabilizers, UV absorbers, IR absorber and light diffuser. These
materials show the required resistance to outdoor exposure and can
be used in form of flexible films as wells as molded inflexible
articles like trays and pots.
[0062] According to another preferred embodiment of the invention
the coating layer has a water uptake of at least 100% per given
coating layer area. Like that, it is possible to provide the
mobility required for an effective emission of the organic biocide
to the target pest or weed by diffusion and/or osmosis.
[0063] Preferably, the coating layer is based on a super-absorbent
polymer coating material.
[0064] Like that, the water uptake and the timing of water loss
during outdoor exposure can be tailored.
[0065] In a further preferred embodiment of the invention, the base
polymer is Corona treated to enhance the attachment of the coating
layer(s) to the base polymer.
[0066] Additive(s), binder(s) and the at least one biocide can be
incorporated in any coating layer of the base polymer. A
particularly preferred embodiment of the present invention is a
Corona treated base polymer comprising at least one coating layer
with a binder, preferably superabsorbers and at least one coating
layer with at least one biocide active ingredient. In a preferred
embodiment, the base polymer further comprises at least one coating
layer with an additive, preferably a hardener (for closing-off). In
another preferred embodiment at least one of these coating layers
further comprises gelatin. In a more preferred embodiment of the
invention all three layers further comprise gelatin.
[0067] Preferably the thickness of the whole coating layer with
binder(s), preferably superabsorbers and preferably also with
gelatin is between 1-100 .mu.m, preferably 5-40 .mu.m, and
particularly preferred 10-30 .mu.m. The whole coating layer can be
produced by coating several layers of binder(s), preferably
superabsorbers and preferably also gelatin for example with cascade
or curtain casting. The thickness of the whole coating layer with
at least one biocide active ingredient and preferably also gelatin
is 0.5-5 .mu.m, preferably 1-4 .mu.m, and particularly preferred
2-3 .mu.m. The whole coating layer with biocide(s) and preferably
also with gelatin can be produced by coating several layers of the
same or different biocide(s) and preferably with gelatin for
example with cascade or curtain casting. The thickness of the whole
coating layer with the additive, preferably the hardener is 0.2-5
.mu.m, preferably 0.5-4 .mu.m, even more preferably 2-3 .mu.m. The
whole coating layer with the additive, preferably hardener and
preferably also with gelatin can be produced by coating several
layers of the hardener and preferably with gelatin for example with
cascade or curtain casting.
[0068] The base polymer has a thickness of 10 to 250 .mu.m,
preferably 10 to 150 .mu.m, and more preferably of 20 to 120 .mu.m,
and even more preferably 20-50 .mu.m.
[0069] In another preferred embodiment of the invention, the base
polymer is preferably on both sides Corona treated and has on both
sides at least two layers comprising at least one coating layer
with binder(s), preferably superabsorbers and at least one coating
layer with at least one biocide. In a preferred embodiment, the
base polymer further comprises at least one coating layer with an
additive, preferably a hardener (for closing-off). In another
preferred embodiment at least one of these coating layers further
comprises gelatin. In a more preferred embodiment of the invention
all layers further comprise gelatin.
[0070] In another embodiment of the present invention the polymer
composite material can withstand at least 12 months of outside
exposure to sunlight and weather. That is independent on whether
there is a coating layer present or not. By having such a minimum
resistance the polymer compound is sure to fulfil the requirements
of the intended use in agriculture as fumigation or mulch film or
as reusable trays for seedling production (nursery trays), for
instance.
[0071] Likewise, the polymer composite material should not be
biodegradable or water soluble. The function of the polymer
composite material should be usable over a long period of time so
that for example no weeds, pests or fungi can harm the plants as
they grow in a field under the protection of the polymer composite
biocide material. Furthermore, the articles of the intended use
like films and trays should be useable over a wider period of time
and should not degrade in one planting and harvesting season, for
example. Especially the mechanical stability of the films should be
kept high because the film should preferably be retractable from
the field and reusable.
[0072] It is within the scope of the inventive polymer composite
material that additional pigments, additives and fillers can be
used which are widely known to the skilled person.
[0073] Another subject of the present invention is a method for the
production of a polymer composite material according to the present
invention including the steps of
[0074] mixing at least one base polymer compound and at least one
biocide active ingredient so that the biocide active ingredient is
incorporated in form of a molecular dispersion,
[0075] forming the polymer composite material in the desired shape
by molding and/or film formation via extrusion or blow molding.
[0076] There are four basic methods used for mixing plastics with
the biocide active ingredients: dry mixer, batch mixer, continuous
mixer, and screw extruder. The selection of the method determined
by the condition of the material, the volume of end product
required, and the sensitivity of the biocide active ingredients to
shear stress and temperature of a polymer melt. The compounding
process includes two stages: (1), mixing the materials and (2)
forming the mixture into pellets, sheets, rods, or lumps for
further processing by molding and/or film formation.
[0077] The present invention comprises therefore a polymer
composite material, wherein the biocide active ingredient is
incorporated in the polymer composite material in form of a
molecular dispersion.
[0078] Alternatively, a polymer composite material according to the
present invention can also be produced by a method for its
production including the steps of
[0079] mixing at least one coating compound and at least one
biocide active ingredient so that the biocide active ingredient is
incorporated in form of a molecular dispersion,
[0080] coating the base polymer compound with the above mixture and
curing the mixture to give a coating layer.
[0081] The present invention comprises therefore a polymer
composite material, wherein the biocide active ingredient is
incorporated into a coating layer.
[0082] The term "coating compound" refers to any possible compound
or compounds that can be used to incorporate the at least one
biocide active ingredient onto the base polymer. Particularly
useful coating compounds according to the present invention are
binders, such as superabsorbers and/or gelatin. In a preferred
embodiment of the invention binders, preferably superabsorbers and
gelatin and a hardener are used as coating compounds. In a further
preferred embodiment the "coating compound" also comprises a
carrier fluid.
[0083] The coating compounds can be applied to the workpiece made
of the base polymer in a variety of ways. Coatings compounds can be
sprayed over the part, or the part can be dipped into a tank of
coating material. Other methods include showering parts with
coatings or rolling parts between large barrels to spread on the
coating.
[0084] Cascade casting or curtain casting advantageously allows the
application of multiple layers, also of different thicknesses, onto
the polymer composite material in a one work step.
[0085] The application of the coating layer is preferably carried
out by curtain coating.
[0086] The method of curtain coating is well known in the field of
photographic films and papers and can be advantageously applied to
the coating of the present invention. Improved methods of curtain
coating procedures that can be used to produce the polymer
composite material of the present invention includes such
procedures as they are described in EP 1 023 949 A1, EP 938 935 A2,
U.S. Pat. No. 5,906,865, DE 195 00 402, and EP 275 015 B1, which
are therefore incorporated by reference.
[0087] In the process of curtain coating, a base film or paper web
is moved continuously by a transport device through a coating zone
and is thereby coated with one or more layers either wholly or
partially by the free-falling liquid curtain.
[0088] In the photographic industry, this process is used, for
example, to apply photosensitive and non-photosensitive coatings.
These coatings comprise mostly multiple layers formed from aqueous
coating solutions which are coated as layer composites in the
liquid state onto the base. The curtain in the curtain-coating
process can be wider or narrower than the base. The base of the
photographic application is mostly a synthetic film or a paper web.
Coating speeds can vary in accordance with the base material and
thickness and with the thickness of the liquid curtain and its
viscosity, for example. In so called high coating speed
applications the photographic coating solutions can be applied at a
base speed from more than 250 meters per minute. The coated base
then passes through a drying device in which the coating solution
is dried. The dry film web is wound up. At this point, the edges of
the web must be dry or else the individual layers of the roll will
adhere.
[0089] With the advantageous possibility of producing the polymer
composite material of the present invention by curtain coating the
base polymer compound with at least one coating layer comprising at
least one biocide, binder(s), carrier fluid and optionally
additives, high production speed and low cost bulk production can
be achieved.
[0090] In a preferred embodiment, curtain coating on a preferably
Corona treated base polymer with a first coating comprising a
binder, preferably a superabsorber and a carrier fluid and a second
coating comprising at least one biocide and a carrier fluid is
conducted. In a another preferred embodiment, the first coating
with the binder further comprises gelatin and/or the second coating
with the at least one biocide comprises gelatin. In an additional
preferred embodiment, a hardener as an additive is added shortly
before curtain coating to one of the coatings. A further preferred
curtain coating method is conducted with a third coating comprising
a hardener as an additive and a carrier fluid. In another preferred
embodiment, the third coating comprises gelatin, carrier fluid and
a hardener as an additive and the hardener is added to the gelatin
and the carrier fluid shortly before the curtain coating.
[0091] Preferably, any of the methods according to the present
invention comprises the further step of coating both sides of the
base polymer compound with a different mixture each comprising at
least one biocide active ingredient. Like that, it is possible to
incorporate different biocide active ingredients, one for instance
for the disinfection of the soil or for the root protection of the
plants and the other one as pesticide and/or fungicide directed to
the surface of the agricultural field.
[0092] As already shortly mentioned above, a polymer composite
material according to present invention or a product obtained by a
method according to the present invention can be preferably used in
agriculture and/or horticulture.
[0093] Especially the use as mulch film, fumigation film, or as
propagation film is preferred.
[0094] Alternatively, a polymer composite material according to
present invention or a product obtained by a method according to
the present invention can be used as propagation pots nursery
trays, and/or harvest trays.
[0095] The invention also relates to mulch film, fumigation film,
propagation film, propagation pots, nursery trays and/or harvest
trays comprising a polymer composite material as discussed
herein.
EXAMPLES
Example 1
Manufacturing of Propagation Films
[0096] Propagation films by coating a polyethylene film with
following additional layers was manufactured by using a curtain
casting machine:
[0097] Film 1:
[0098] Base: Corona treated 100 .mu.m thick Low-density
polyethylene (LDPE) polyethylene film
[0099] First layer: 9.36 g/m.sup.2 superabsorber S1 (flexible
absorbent binder composed of: 20-40% by weight Sodium Polyacrylate
(CAS-No.: 9003-04-7), 2-5% by weight polyethylene glycol (CAS-No.:
25322-68-3), water (CAS-No.: 7732-18-5) dissolved in 53.40 g
water
[0100] Second layer: 9.36 g/m.sup.2 superabsorber S1 dissolved in
53.40 g water
[0101] Third layer: 9.36 g/m.sup.2 superabsorber S1 dissolved in
53.40 g water
[0102] Fourth layer: 9.36 g/m.sup.2 superabsorber S1 dissolved in
53.40 g water
[0103] Film 2:
[0104] Base: Corona treated 100 .mu.m thick Low-density
polyethylene (LDPE) polyethylene film
[0105] First layer: 9.36 g/m.sup.2 superabsorber S1 and 3.12 g/m2
gelatin dissolved in 53.40 g water
[0106] Second layer: 9.36 g/m.sup.2 superabsorber S1 and 3.12 g/m2
gelatin dissolved in 53.40 g water
[0107] Third layer: 9.36 g/m.sup.2 superabsorber S1 and 3.12 g/m2
gelatin dissolved in 53.40 g water
[0108] Fourth layer: 9.36 g/m.sup.2 superabsorber S1 and 3.12 g/m2
gelatin dissolved in 53.40 g water
[0109] Fifth layer: 2.34 g/m2 gelatin dissolved in 27.53 g
water
[0110] Sixth layer: 1.20 g/m2 gelatin
[0111] 1.33 g/m2 hardener H1 (formaldehyde, concentration: 10% in
water; coating amount 0.086 g hardener H1 per g gelatin). Gelatin
and hardener are premixed shortly before curtain coating with 28.20
g water
[0112] Film 3:
[0113] Base: Corona treated 100 .mu.m thick Low-density
polyethylene (LDPE) polyethylene film
[0114] First layer: 9.36 g/m.sup.2 superabsorber S1 and 3.12 g/m2
gelatin dissolved in 26.70 g water
[0115] Second layer: 9.36 g/m.sup.2 superabsorber S1 and 3.12 g/m2
gelatin dissolved in 26.70 g water
[0116] Third layer: 9.36 g/m.sup.2 superabsorber S1 and 3.12 g/m2
gelatin dissolved in 26.70 g water
[0117] Fourth layer: 9.36 g/m.sup.2 superabsorber S1 and 3.12 g/m2
gelatin dissolved in 26.70 g water
[0118] Fifth layer: 2.34 g/m2 gelatin dissolved in 27.53 g
water
[0119] Sixth layer: 1.2 g/m2 gelatin, 1.33 g/m2 hardener H1
premixed shortly before curtain
[0120] coating with 28.20 g water.
[0121] After coating, the films were dried.
Example 2
Mechanic Stability of the Films
[0122] Than, the films prepared according to example 1 were soaked
for 10 minutes in distilled water. Subsequently, excessive water
was drained and the mechanic stability was tested by washing-up the
soaked layers with flowing warm water. Whereas the superabsorber S1
layers dissolve from the polyethylene layer in film 1, the
additional layers in films 2 and 3 do not dissolve from the
polyethylene layer.
Example 3
Manufacturing of Fumigation Films with Biocides
[0123] According to similar methods as described in example 1,
following six fumigation films were manufactured with the following
final coating thickness after drying
[0124] Base: Corona treated 100 .mu.m thick high-density
polyethylene (HDPE) film
[0125] First layer: 6 .mu.m superabsorber binder
[0126] Second layer: 6 .mu.m superabsorber binder
[0127] Third layer: 6 .mu.m superabsorber binder
[0128] Fourth layer: 6 .mu.m superabsorber binder
[0129] Fifth layer: 3 .mu.m gelatin with herbicide
[0130] Sixth layer: 3 .mu.m gelatin hardened
[0131] Following different herbicides were introduced in the fifth
layer: placebo (film 1), aclonifen (150 mg/m2; film 2),
ethoxysulfuron (6 mg/m2; film 3), isoxaflutole (10 mg/m2; film 4),
benfuresate (150 mg/m2; film 5), glyphosate (200 mg/m2, film 6),
Halosulfuronmethyl (5 mg/m.sup.2, film 7).
Example 4
Manufacturing of Fumigation Films with Biocides
[0132] Low density polyethylene were dry blended with 7 percent by
weight of a commercial stabilizer LDPE masterbatch with Titanium
dioxide pigments and HALS UV stabilizer, e.g. PLASTWITTE PE 7344
from Cabot Deutschland and the specified amount of, the selected
herbicide, extruded and chopped to form molding pellets. The
molding pellets were placed in a standard blow molding apparatus
and the thermoplastic composition was blown into a film in
accordance with conventional procedures at temperatures between 160
and 240.degree. C..degree. depending on the decomposition and/or
boiling temperature of the selected herbicide. Sample sections of
the various films of uniform surface area and uniform 100 .mu.m
thickness were used for all tests.
[0133] Films without herbicide (film 8), and with Ethoxysulfuron (6
mg/m2; film 9) and benfuresate (150 mg/m2; film 10) were blow
molded from the above mixtures and tested.
[0134] Table 1 indicates the physicals properties of the films
according to example 8, 9 and 10.
TABLE-US-00001 TABLE 1 ASTM Method Units (SI) Typical Value Resin
Properties Example 8/9/10 Properties Melt Index D 1238 g/10 min.
1.8/1.8/1.8 Density D 1505 g/cm.sup.3 0.923/0.922/0.922 Melting
Point -- .degree. C. 110/110/110 Film Properties Example 8/9/10
Tensile Strength @ Break MD D 882 % 4000/4010/4001 TD D 882 %
3400/3402/3398 Elongation @ Break MD D 882 300/298/301 TD D 882 %
500/500/500 1% Secant Modulus % MD D 882 % 26000/26100/26002 TD D
882 % 30000/30000/30000 Dart Drop Impact D 1709 g 90/89/91 Strength
Elmendorf Tear Strength MD D 1922 g 360/360/359 TD D 1922 g
200/201/200
Example 5
Improvement of Weed Control
[0135] Soil filled trays with a range of weeds including the key
problem weeds of CYPES (Yellow Nut Sedge, Cyperus esculentus), and
CONAR (Field Bindweed, Convolvulus arvensis) were used for a glass
house trial with the plastic fumigation films (comprising biocides)
manufactured according to example 4.
[0136] Soil was filled in to plastic trays until they were
approximately 3/4 full and then the soil lightly compressed. Even
amounts of CYPES and CONAR weed seeds were then sown out on several
sets of these trays and then the seeds covered with soil until the
trays were completely full. These filled trays were then covered
with the different plastic fumigation films and as a control an
untreated placebo plastic film. Light weights were placed on the
plastic film to ensure that the film was not pushed up or away via
weed growth.
[0137] The filled and covered trays were placed in a glasshouse
with a 12 hour day and 12 hour night regime. Day temperatures were
24.degree. C. and a relative humidity of 60% and night temperatures
were 16.degree. C. also with 60% relative humidity. The light
intensity is up to 60,000 Lux. The plants were irrigated via flood
irrigation (water from below) daily so that good growth of the
plants could be assured. Plant growth was monitored via 2 reps of
each weed species that were not covered with plastic film.
[0138] After 4 weeks the weights and the plastic films were removed
and a visual assessment of the weed control was conducted. The
trays covered with treated plastic film were compared to the trays
covered with untreated plastic film. A mean of the two reps per
treatment was made and is shown below in table 2. Values given are
in percent 0=No efficacy; 100=Complete Kill.
TABLE-US-00002 TABLE 2 Biocide concentration % Efficacy Plastic
Sheet kg ai/ha CYPES CONAR Placebo Film (film 1) 0 0 Aclonifen
Folie (film 2) 1.500 30 37.5 Ethoxysulfuron (film 3) 0.060 96 97
Isoxaflutole (film 4) 0.100 55 95.5 Benfuresate (film 5) 1.500 98
97.5 Glyphosate (film 6) 2.000 42.5 67.5 Halosulfuronmethyl (film
7) 0.053 96 65.0 Placebo Film (film 8) 0 0 Ethoxysulfuron (film 9)
0.060 89 90 Benfuresate (film 10) 1.500 91 92
[0139] All films comprising biocides showed medium to strong
inhibition for both weeds over a period of at least 4 weeks.
* * * * *