Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
wo 94/23s73 2 1 6 O 8 6 7 PCT/US94/02555
IlILE
WATER-SOLUBLE FIBERS AND NETS AS
AGRICULTURAL FORMULATIONS
The present invention relates to the use of water-soluble fibers cont~ining
5 agriculturally active ingredients as agricultural formnl~tio~. The fibers can be in
various embo~lim~nt~ such as solid fibers co.~ g active ulgl~.;li~,nl dis~cl;,cdtherein, or sheath and core fibers wh~lGul a polymer sheath ~ullounds a core of
active ingredient. The fibers are col~ ;ul~,.,i into ropes, nets, or other physical
forms.
A sealed water-soluble bag co.~l;.;.. ;.~g ~gricllltl-rally active ingrerli-~nts, is
disclosed in U.S. 5,080,226 which reduces worker CApO~iUlC to ~grit~nltllr~lly
active iny~re(1if ~ and elimin~tes the need to dispose of cont~min~te~l O~ W1~S.However, water-soluble bags do not provide a means for variable unit p~ck~ging
A single ~ri(~nltnrally active ulgl~di~ G;l in a water-soluble polymer
sheet, as disclosed in U.S. 3,299,566, addresses the need for variable unit
p~rlr~ging but the dissolution rate of the sheets can be too slow in a water mi~tarL to meet a grower's needs. Neither of these water-soluble ~olylll~
formlll~tion~ offer ull~lu-vG~llc.~ls over CO11VG-~I;O~11Y sprayed formlll~tion~ in
re~lllcing off-target movG~llc~ll (aerial spray drift and mov~lc.ll in the so;l) or in
20 avoiding mi~ tank clea,luul concPm~.
WO 89/01284 (li~closes a water-~ ....e,~lble sheet ~ ~ed from water-
in~olllkle polymer co~ g bodies ("buttons" or "beads") of ~olylllcr which
contain a 2,6-dilu~o~-iline pesti~i~p~ Disposal of the water-~ -..-e~ble sheet is
l~luil~d.
U.S. 3,299,566 discloses ~ ;o.~ of p~sti~i(les within p~"rul~ d water-
soluble .~;l.P~ and appli~tiol- of this sheet to the soil. However, the sheet uses
e~cess polymer per unit area and is clumsy and easily blown about by the wind
(creating a secc~ y hazard). Thus, there is a need for an ~griellltllral
forrnlll~tion that provides variable unit p~ ging, red~res off target mo~,. .ll-,nl,
30 avoids mi~ tank cleanout problems and is easily di~osa~lc without Cl~ ating
secondary haLards.
SUMMARY OF THE INVENTION
The present invention colll~lises an ~gri-~llltllral col.l~osilion CC~...pl ;~;. .g at
least one water-soluble polymeric fiber wh~ re~l at least one ~gri~ r~lly active35 ill~ is cQn~ Gcl within the fiber. The fiber can have the ~riCIlltllr~lly
211~.~,8~7
WO 94/23s73 ~ PCT/US94/02555
active in~ di~ nl uniformly dis~cr.,ed or dissolved tnerein. ~llc~ ;vdy, the
fiber is in the form of a polymeric sheath of at least one layer Y,u,luunding a core
co.l-plisi~lg the agricllltllrAlly active ingredient. The polymeric sheath can also
contain one or more Agrit~lllhlrAlly active ingrerlients~ or can co~ e mnltirle
5 layers, each said layer Co.~A;.~i..g at least one Agricllltnrally active ingredient. The
Agricllltllral colll~osilivll of the present i~lv~ ioll employing one or both of the
above-descril~ed fibers is configured into various physical forms. For e~mple,
two or more fibers can 'oe configured in the form of a rope or net wllc,~ each
fiber collt~ls the same or distinct active ingre-lients. Thus, Llcc, ~olalion of10 L.co~ alible active ingredients in one formulation is possible. Fur~er, such nets
or ropes can be p~.~ral~ d into unit dosages easily sep~ e~ for use in desired
a~r~liate q~lAnthies. The present invention further co...l.l;~s water-soluble nets
of random or unirollll confi~ ali~"l CO,.~ g A~riclllhlrAlly active ill~;r~ ts
~lC~ by the creation of voids or holes in water-solublc film llcol~oral~lg
15agriclllh~rAlly active ingredients within the film matrL~c.
BRIEF DESCRIPIION OF THE FIGU~P~:
Figure 1 is a cross se~l;o"Al view of one fiber of the present i~ io
wh~ l~LI A is an A~ri~lllh~r~lly active i-~ ,dielll and B is a polymer sheath.
Pigure 2 is a cross sc~l ;o,~A1 view of ~Ivtll~. fiber of the prescnt Ll~,.,nli
20wL~tLl A is an Agriclllhlr~lly active ingredient and B is a poly~llcl matri~.
Figure 3A is a plane view of a woven net of the present invention of
l".;rV~ COn*~ J~
Figure 3B is a plane view of a net of the present Ll~ ion of r~n~lom
confi~,--. ~1;.31,
25Figure 4 is a scnn~ elccllun micrograph of a net of the present U~ ion.
The fiber diameter ranges from less than 1 ,u to 10 ~.
r~ETAILED DESCRIPIION OP TH~ ~IION
~ ri~lllhlral colllposilioll of the present ,.lv. nlioll can take the form of a
fiber of a polymeric sheath ~u~uull~illg a core co~ 8 the active L~ lielll.
30 This type of fiber is ~,r~ d to hc~L~ as a "sheath and core" fiber and is
. Al~ in Figure 1. In addition, the present ill~ ~lliun coll-~,ises ~riclllhlralcolllposilions of fibers wL~.cill the agriculturally active in~.~,.,l;...~l iS
hûmogeneously dissolved and/or dis~ ed in the polymer which forms a
co..~ .,ous solid matrix. This type of fiber is referred to h~.ci lart~. as a "solid
35 filled fiber" and is illt~ cl in Figure 2.
Wo 94123573 ~ 1 ~ 0 8 6 7 PCTIUS94/02555
A "rope" is de~m~-l herein as two or more fibers, sheath and core and/or
solid filled, Lll~,lwu~cd to form a larger cylin(lric ~1 form wL~lcil~ the average
distance b~ ,cn the fibers is less than the fiber diameter. Fibers CO~ g an
~griçultllrally active L~gl~,dicl,t and comb;-~ ;ons of such fibers in the form of a
S rope are useful to safely apply agriculturally active in~l~di(,nls for either pre- or
~o~t~ - ..e - g~nl Ir~all"cnl. The proper dosage of active Llgl~diwll is me&~urcd per
unit length of fiber or rope. The sheath and core fibers and ropes ~r~p~d
Ih~rern,lll wilhoul any ~griçlllhlrally active Llg,~,di~nl in the sheath are esreci~lly
eLrc~liv~ in providing worker safety.
In a pr~,.llcrg~,nl appli~tion, one or more fibers or ropes are laid in a
furrow during seed pl~nting For ~mrle~ the appli~tion may be ~ccomrli~h~l
by unwinding a roll of the fiber(s) or rope behind a ~roul~Lig and covering it and
the seed with soil. Dissolution of the form~ tiQn polylllcl and release of the
active L,~;l~ic-ll are ~ccc - .~ cl by . ~lyL~g water (by ground rig or irrigptit)n)
15 or by rain. ~ ;vdy, applit~tion can be acco...pli~hP.~l by "shooting" the fiber
or rope from a series of ~l,oot~lg a~ tuS mounted across a ground rig wL~r~ a
nllmb~!r of p~rpll~l fibers or ropes are shot onto or into a canopy of plants.
Rdease of the active ingredient is ~CCO~ hC~1 by ~r~~ water at the same
time or after the fibers or ropes are applied.
In a ~i,t~. . .r.. g.. ~l apr~ tinn, the fiber(s) or rope(s) is l~lct~ ,d into a mi~
tank of water, WLC.~iU~ sollltion occurs quicldy bcc~ c of thc high surface areaof the fiber(s). The ~ litinn to the mi~ tank is ~l~,f~ co~ l.ecl by
'~hOUL;~ the fiber or rope from an ~u~, e.g., a hand held "gun," cc...l;~ g
rolls of the fi~m nlPtion The fiber or rope may be propelled r~llmPtirPlly or by25 ~;~il~g rollers. E~Gr~bly, a pc,~ r- ~5~,nl s~ is made in a spray
injection system wh~,r~ a fiber or rope is coll~ d into closed ch~mbers
wllcre..l the polymer rapidly dissol~s in turbulent water and the agrirllltllr~lly
active i.,~ emerges in an aqueous spray, e.g., from an aerial rig. In this
way a more closed system than a mi~ tank is used, and co~ about worker
30 G"~OSul~ and tank cleanout are re~lce~l The fibers and ropes of the present
invention provide a hi~ ,lo Ul~lOWIl way of injecting a solid formlllPtio~ with
ulurulll- metering and rapid dissolution WiLIlUUl producing contPminPterl waste
p~ ging The fibers or ropes can optionally contain air to aid in floating.
The agricultural colllposilion of the present invention can also be in the
35 form of a net which is ~lefin~cl herein as a plurality of intermingled~ overlaid, or
WO 94t23573 216 0 8 6 7 PCT/US94102555 ~
willcd fibers wh~ rth1 the average tli~tAnce b. I... e,. the fibers is equal to or
greater than the fiber diameter (i.e., the aspect ratio is greater than or equal to
one). The fibers can be in a random or ordered ~~ c.~ within the net. Some
nets of the present invention are iUu~LIaled in Figures 3A, 3B, and 4. Nets can
5 also take the form of a water-soluble filled film which contAin~ a plurality of
holes such that the open space of the net is equal to or greater than the solid area.
FiUed films are sheets of polymeric material having an A~rirllltnraUy active
L.gr Lenl dissolved and/or di~ cd within the polymer matri~.
The nets are useful to safely apply ~gricllltllrAlly active L~ di~ nl~ for
10 either pre- or postemergent tl~at~r ~ The proper dosage of agricllltllrAlly active
in~l~ Lcnl is ..lcasu,~d per unit area of net.
For e~cample in a preemergent application, a roll of netting is u--w~und
behind a ~,,o u~ig onto the surface of t-h-e ground after, or ylGr~.~bly during, seed
plAnting Release of the active in~ d;~n~ is acco...~ h~ by s~ lg water
15 (optionally with fertilizer and ~ ), by irrigption~ or by rain or dew.
In the most ~ E~l. d postemergent a~liratiQn, a roll of netting is u--woulld
behind a ground rig over the e "llCL~ g crop. Release of the active in~ nl is
n-, o...~ hçd by spraying water at the same time the net is unroUcd from a
ground rig. In this way the partially di~ol~e~, gel-like net is d~posit~l on the20 foliage. The deposition: (l) aids s1 ;. L ;. ~g of the active i.-~5~.1 to ~e target
area, (2) helps ~r~ . nl off-target active from re~chir~ the ground, (3) begins
release of the active L~ iie"l, and (4) helps anchor the net du~ing unrolling.
Spray drift is not a Co~G~ ~, since only water (or water plus fertili~/ ..~1. ;- -~1) is
sprayed. Narrow nets can be placed l~h.~ IOWS for control of pests in regions
25 ;" " "GrliA1~ 1y ~j~c~ l to the crop.
Simil~rly, the fiber nets of the present i,.venli~ll can be spread over
individual trees in ol~ ds. Tl~ c.ldous drift ~.oblc.,-s ar~ c.~co! -- .tcl~cl when
co -~. ..1 ;u.~l agn~ r~l co -~t,osil io~S arc spray blasted onto trees. However,
only water is sprayed with the net, and IL~.crolc spray drift probloms with the
30 ~ric~ r lly active ~ L~nis do not e~ist.
In a~ L JI~O~ ,nl appli~Ation of the fiber nets of ~e present
invention, unit sheets of nets (e.g., one square meter of net per hectare) are
introduced into a mi~c tank of water and ~ r. ~l~ d in a con~ onAl
manner. ~lt~mAtively, narrow strips of netting can be ll.Ct~ .cd into a mi~ tank or
35 injectionlineandspr~dina COllV~ l;v~Al m~nn~r. Rapidli.csol1lti~nis
21~8~7
wO 94/23573 PCT/US94/02555
s
re~ii7e-l, because of the high surface area of the net. A Auncr~ ll. d net for mi~ tank
application cc,~ es a number of fibers fA~led with air along with the fibers
co.~ g the agriculturally active ingredient such that the net floats, and
IL. rtrc,lc dissolves rapidly. A net which sinks in the mi~c tank can stick to the
5 bottom and dissolve more slowly.
The composilio.ls of the present invention may be packaged as rolAs or
sheets cc ..~ Pd within water i~Au~ ~ vious packages. In the case of the sheath and
core fibers wl.ertA,~ the sheath lacks an active ingredient, the packages are
co~l;....in~te~l and require no special means of disposal. For cases wl~leill the
10 active ulgl~di~ may reside uncodted on the surface of the fiber (e.g., the solid
fAlAed fibers), water-soluble fAlm linings within the pfl~ ges may optionaUy be
used. This lining may be added to the mi~ tank, dissolved and ;~AU1~CdA~
The ~griclllhlr~lly active ~ SICIA&I~ which are suitable co--t~ for the
fibers of the present invention co. ~ '1" ;~e Au~sl ;ciflf s such as herbicitl~s, filngici-l~s,
15 in.~ecti~ ides, b~cteri~i~lec, ~c~rici-l~os, and biological pest control agents, as weU as
plant growth reg~ tors, and form~ te-l COIIIAUO~;~ io,~.c thereof. The ~gri~nlt~lr~lly
active in~.. .1;. .1~ can be in the form of 1;~1An;~1~, gels, or solids. In short, any
rhf~mic~l or biological active i.~ Le.-l can be packaged using the fiber delivery
system, provided it does not dAss(Jl~ the water-soluble poly~ .c. or bcco---e
20 de~Auliv~Atf d by the polymer.
A~camples of suit~ltle ~gricllltllr~l pCCl ;CiClGS in~ly~le hAl~ cidcs such as
" ;~1-0. r. ." ~ m, alr~ inf, l~f .~lA~o~, bromacil, bromo~cynil,
AYI~ v ; e, ChAorAmbç~, chAolvAuAulA~ chAorotuAuron, clom ~rnn~,
~;y ;~ f ~ " ~ m e. 1 ;1 .h ~ ~ ~m b~ dAc~AlAorbeAqAA, hl orprop,
25 ~lirh~n~mi-l, diAuluAu~hyn, diuron, ILi~AlleluAun~ fenac, ~AluAun~ fluometuron,
fll..~ fomesafen, ~lyAuhosale, 1~ o.~e, im~ c~ t~.~, im~
im~,~ Ih~l~yl~ io~ynil, ASOAUrclluA`~ isoui~on, i~o~n~ karbutilate, lenacil, 4-
clAlAoro 2 methyl AL~ llO~y ~C~tAc acid, 4 [(4 cAhAûro o tolyl)o~y]l,ulylic acid,
mçfl--it~ e, IllGlh~h.~.l,ll.i~llron, m~th~role ll.ehil,u;~Au, monuron, n~pt~l~m,
30 1l bUAVn~ nitralin, I-G-~ r~ ûl~ oAryzaAin,pPrflllitlone,Auh~ e~ A~,picloran~A,
prometryn, Aurv~ e, AuluAua~AAle, pyrazon, si~Aulon, ~im~7in~, le~u~AAiuA~vll~
terbacil, le.luulllylazine, telbulAyll, triclopyr, (2,4-dichAoA~vAL~ noAy)acetic acid, 4-
(2,4-dichloA~oAI~ o~cy)butyric acid, and suArollyluA~as such as ~hlor~ulfilron,sulro..leluloll~ çhlol ;...u.Oll ethyl, met~nlfi-ron methyl, methyl 2-[[[[(4,6-
35 rlimçtho~cy-2-pyrimi-linyl)-amino]carbonyl]-amino]sulAfonyl]-6-(1AirAuulvAIll Illyl)-
;216~86 7
WO 94/23~73 PCT/US94tO2555
3-pyri~lin~c~rboxylate, eth~metsulfilron methyl, tri~ lfilron, ethyl 5-[[[[(4,6-
dimethoAy-2-pyrimidinyl)amino]c~b~ yl]-amino]sulfonyl]-1-methyl-lH-
pyrazole~-c~l uAylate, N-[[(4,6-dimetho~y-2-pyrimidinylamino]carbonyl]-3-
(ethylsulfonyl)-2-pyridinesulfon~mi-le, lhif~ -~s~lfilron, ILib~ u~ùll methyl,
5 bensulfuron methyl, nicosulfuron, methyl 2-[[[[[4,6-bis(difluoromethoAy)-2-
pyrimidinyl]amino]c~Ll,ollyl]amino]sulfonyl]-b~oalc, methyl 2-
[[t[[4-dimethylamino)-6-(2~2~2-trifluo~ "y)-l~3~s-triazin-2-yl]amino]
c~l,ullyl]amino]sulfonyl]-3-methylbe~l~.oatc~ N-[[(4,6-dimethoAy-2-
pyrimidinyl)amino]c~l,-)llyl]- 1 -methyl4-(2-methyl-2H-tetrazol-5-yl)- lH-
10 pyrazole-5-suLfon~mide, and salts thereof. F-~mples of ~ui~ le l;~y~;cid~s
include carbPn~1~7im, ILLUi~ll, dodine, chloroneb, cymo~anil, captan, folpet,
thio~ n~ -methyl, Illiab.~ .1;.,.ole, chlûroth~lonil, ~lichlor~n~ captafol, iprodione,
vinclo7.olin, k~lg;~ y~ thiq~limrnol~ flntti~fol~ flnsil~ol, h~s~co..A,.ole, and..ol. An eAample of a suh~hle b&ct~ - ;ci-lc is ~AylCtL~CycLlc dihydrate.
15 F~mrles of suitable ~l ~rici~l~s include h~ ~thi70~, o~ythis)~:lui.~u~ orhlor,
and cyll~ ;ll F~ S of ~ ble in~eCsici~l~s include C~b~ ~l, carbyl,
tLLodicaLb, d~lt~methtin, and tetrachlolvil~hos. F. ~mrles of suitablc biological
pest control agents include PL~C;~ h... ;.~ and baculovirus.
E'~cf~ d agricllltllr~lly active ;.,~ are sulfol~ a h- bi. ;dGs and
20 salts thereo
Each of the types of embo~ may be used to introduce two or more
active irl~ s, even if they are ûrd;~ ;ly ;.~cv~.p ~ le to~ll.Fr in the same
form~ ti~n, since they are s~ n-l from each other in L~divid~-fil strand~ or
layers of polyllle.. E~amples of illco..~ lc pairs of crop ~rot~,clioll ch~mir~ls
25 which can be used in the present i~ ion in~ e- b~ns~lfnron methyl and
molinate; (2,4-dichlvlu~hmo"y)acetic acid and ll.;r,--~--lfilron methyl; (2,4-
dichlo,ù~h~nvAy)acetic acid and methyl 2-[[[[N-4-methn~y-6-methyl-1,3,5-
L,i~hlc-2-yl)-N-methylamino~c~l,vllyl]amino]sulfonyl]l~ ~o-~t_, (2,4-
vichlvlv~ llv~y)acetic acid and metslllfilron methyl; maneb or m~ o,~ and
30 benomyl; ~ y~hosdle and metsulfuron methyl; tralo..~r~ and any
o~ u~llo~l~h;~le insecticicle such as mono~rolophos or ~lim~ll.o~le; bromo~ynil
and N-[[4,6-~1imetho~y~y . ;~ ine-2-yl)amino]c~l~ollyl]-3-(ethylsulfonyl)-2-
pyridine-s~lfor-~mi~; bromoAynil and methyl 2-[[[[(4-methyl~-1l.clhoAy)-1,3,5-
triazin-2-yl)amino]ca~bullyl]amino]-sulfonyl]b~..,u;.lc; and bromo~cynil and
~WO 94t23s73 21~ 0 8 6 7 PCT/US94/02555
methyl 2-[[[[N-(4-1nell,uAy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]-
Ca~l~ul~ ]amiIlo]sulfonyl]~ t~-
The compositions of the present invention employ polymers which are
soluble in cold water, fiber-forming, and bio~le~ ole. These ~ ;cs allow
S the pf~l)~alion of the fibers, avoid residual polymers in the soil and f~nilit~te
quick release of the active u1~71~ dic"l in the ;...~c li-~tc locus of the target area.
Cold-water soluble grades of polymers may be used for both pre- and
po~7~ nl application. Somewhat slower dissolvillg polyllle.~ and/or thicker
fibers may be used in fonn~ tions for p.~.l.e.~c.ll appli~tion
Suitable water-soluble polymers include homopolymers or salts or
copolymers thereo F~mrles of such polymers are polyv~l~l alcohol (PVA),
polyethylene oAide (PE~O), water-soluble ~ul.~L~uled cellulose (e.g.,
hydluAylulu~yl methyl~ellnlose, methyl cellulose, calbu~yll~clllyl celllllose,
hy~o~ yl cellulose, c~l~u~y methyl l-y&u~ ylc~lllllose), starch, gdatin,
15 polyvinyl pyrroli~1on~, polyacryl~mi-le7 polyacrylic acid, and poly...e~ -ylic
acid. PEO and especially PVA are pl~f~ d.
The fibers used in the co l~)i~;l'~'"'~ of the present L,~,~nlioll up~iollfilly
contain one or more adjUV~l~:j. Adjuv~,~7 snit~ble for use herein are well knownin the art and include water-soluble bintl~r~, e~c;~u~ 7, surfactants, ;,~ del-
20 ~ L~ , dcfo~- n~-x, and water-soluble pl~ . Polyols are yl~ r~ d
pl ~tiri7 -rs for the fiber-formin~ poly",el ~ i n.~l..-l;. ~g pol lylcnc glycol,
~ly~.`~l~ and ~-o.~ . r~vl~ with long chain ethylene o~cide groups.
Solid filled fibers wl.~ the ~gri~ hlr~lly active h~ t(s) is ~ UG ~1
and/or dissol~ ~d in the water-soluble ~oly,-lc~ may be ~ d by e<.ll~ 1 ;."~
25 sollltion- or melt-~:....;..g ~roccP -~s. Both prwcss~ s are well known h the~iyllll.C~iC fiber llldU~'Lly. The melt-~,ui-~ lOCGSS il~vulv~,S eAl,usion of a
polylllt,r melt through a capillary followed by cooling. The SOlU1;01- ~lJ ~ g
ùccss illvVl~,S c~ u;,ioll of a sol.-l;o.~ of the poly ,cr in an inert solvent
followed by drying. The melt ~,u;....;~g Ic~ ,c is ~l~Ç~ cc.l~,sc a solvent
30 l~CO~ y step is ~voided and some of the ~grit~l-lhlrally active ill~l~ dk~ easily
degrade in the ~ul~s~.lce of solvents (e.g., hot water). In the ~rcf~.l~l ~lucess, the
amount of solvent, the IC 11PC `~U1G, and the t*)OSul~ time to solvent are
minimi7~(1
Filled sheath and core fibers are ,urcp~d by melt-spinnin~ or co-e~ctrusion
35 processes. The multi-layered type of fiber (i.e., those co.~l~;..;-.g co.~e~ ;c or
WO 94123s73 't 21~ ~ 8 6 7 PCT/US94102555
acentric sheaths) is ~r~ d by co-e~ctrusion. The co-e~ctrusion process is also
well known in the :~ylllh~ lic fiber illdu~LLy. The ~loce~ involves e~ctrusion of a
polymer melt through a capillary which is ~u~ ullded by a second stream of
polymer melt flowing through an outer co-a~ial co..~ 1. ;c or ~c~ntric capillary.
S The outer capillary can be ~ unded by a third stream of polymer melt flowing
through a third co-a~ial capillary. The fiber formcd ~ b~ co...l~ ;ccs an outer
most layer, the outer sheath, an inner sheath l~nealll the outer sheath, and a
central core.
The cores of the sheath and core fibers can be flled with active ~ di~
10 alone or active ~ Len~ d and/or dissol~i in a water-soluble binder.
The binder can be any water-soluble binder norm~lly used for gr~mll~tion of
~gric~ t lr~lly active ~n,Lcllls (e.g., sugars and lignin~lrollat"3). M~ blc
binders, esreci~lly low ..~cll;..g binders such as pol~ ~lylcnc o~ide or
pol~ llylenc glycol, are ~l~f~ d bccaus~, solvent removal is not ~rc~--y.
Filled fiber nets can be ~,~p~,d by jet d~ t~vd solntiorl spinning, drying
the fibers in a current of hot air, and dh~ lly l~ c fibers in the form of a
net over a screen or COll~- ~or belt, as dcs~ Kr1 in U.S. 4,963,298 herein
~llcol~or~hd by ~ nce. ~lt~ .ly, the nets can by ~z~d by
COl.~ ;o-~l means such as . CaVlllg or k ;~
The amount of agrirlllhlr~lly active ill~n,L~ (s) in the fibers range from
about 0.0001 to about 50 weight percent, based on the total weight of the
colll~;lioll. The ~l~,f~ d amount for ffbers ~ t~1 for direct apl>~ ;ol~ is
from about O.OOOl to about 5 weight p~ cenl, while a range from about 5 to aboutSO weight p~r~,ll is plcrcll~d for fibers to be applied using mi~c tank or injectirn
m~thrJdS. At least 35 weight ~rc.,.ll polymer, based on the total weight of the
coll.po~ilion, is l~U~ d for fiber illt~il~ .
Fiber ~ may range from about 1 micron to about 1 cm. A ~ ct~ -
range from about 1 micron to about 0.25 mm is ~>~cfcl~ d for fibers applied by
mi~ tank or injection ..~rll.o~l~ in order to speed d~sol.-l ;o.~ A fiber ~ -,t ~
30 range from about 0.25 mm to about 1 cm is ~l~r~ d for direct, non-mi~ tank
applied fibers. The fibers in the nets pl~pal~d by jet attem~t~rl ~pinning typically
have ~ ctc~ ranging from about 1 to about 100 microns. Larger L~llctc
fibers are ~ d by melt CO-CAI1U~iOn terhnillues from a melt c~llud~ l.
The filled fibers fAk. ;r~- d into nets have a m;--;-------- tensilc ~ h of
0.05 N/m/g/m2. Net tensile ~LIc~ ll is .. ~e~ d by cutting a 12.7 cm square
~WO 94/23573 2 1 ~;0 ~ 6 7 PCrlUS94102555
sample of the net and weighing it to give the basis weight. The sample is then
mounted in an Instron tensile tester available from Instron Co11,pa ly, lO0 Royall
Street, l~nton, MA 02021, and the force and r~t. ~ uu~ d for breakage is
dPtPrminPtl through a Cc,ll1pul~. Aided Tensile Testing System (CATI S) data
5 acquisition system.
load at m~simllm force (N)
Tensile strength (N/m/g/m2) = basis weight (g/m2) ~ width (m)
Nets of the present invention can also be ~ h. d from f~ed films by
lO creating a plurality of holes such that the void area is greater than or equal to the
f~ area (followed by optional ~ tcllil~g). The nets can be ~.~p~d using
~Icll1ods known in the art for p~ ;. .g and ~1u._tchi,~g polymer films (see
Encyclopedia of Polymer Science and ~ 5;..~ . ;..g, Volume 6, John Wile
Sons, New York, pp 375-377; and Kirl~-Othmer Encyclopedia of (~ mi~
Technology, 3rd ed., Vol. 16, John Wiley ~ Sons, New York; pp 833-834). The
film may be ~c.rorated by a knife, needle, or pin roller. The ~ d f~ may
then be drawn ~ lly by con~ 1 means. Filled films are ~l~pa.~d as in
U.S. 3,299,506 and British Patent 2,095,558. Each of dlese patents ~ clos~s a
water-soluble polymer COl~ 3 a ....;ru....ly ~ e~ c~l in the form of a
20 thin flat film which can be torn or cut into 1- ca;,ul~d scc1;o.~ for dd~ of the
rll~mic~l co in the water-soluble poly1~cr.
The water-soluble f~ed film is made by d~solvil-~ the poly~cr being used
in water followed by ~ l;l ;ol~ of and mi~ing of the ~gri~lltnrs~1 ~,l.. i<~llL. ,~ ~. ilL and removal of water to form a solid ~oly.. cr film with r"5. ;~ ---1l .-.; 1
25 ~hrmic~l d;.~.~ed therein. If the ch~mic ~l is a liquid, it can be added dilc~tly to
the di~sol~ ~ d polylllcr. The comb;~ results in an oil-in-water ~m~ ion- A
low-...P~ g wa~cy solid ~ric1lltllr~l ch~mit-~l is heated above its --c11;-~ point
and added to the polymer sol1ltion- A ~uwdc. can be added &~lly to the
polymer sol~ltion or by m~king a sluIry in water and adding it to the polymer
30 soll-l ;o~ The comb;~ ;o-~ results in a di~c.~ . The h~ C of ~LssOl~rcd
pûlymer and ~ ch~mic~l iS cast into a film.
The rçsnlt~nt water-soluble film may contain from 1-65% of an s~ cn1tllrz~
chemical based on the weight of polymer plus agricnltllr~l rhPmic~1, to provide
the amount of h-~.mic~l desired for particular ~rpli~ti~n
21fiO867
W0 94123S73 ~ PCTIUS94/02555
The fibers, ropes or nets for relç~ine the acthe iny~ ielll in a mi~ tank or
for applic~tio~ over the crop diDsolve in water in ten mimltes or less, ~l~,î~ly S
minlltes or less. Fibers, ropes, and nets intçn~led for other appli~ ~tion~ (i.e., to be
layed in rull. WD), dissolve in 30 minlltes or less. Di~sohltion is .llca~..r~d by
adding a 15 mm length fiber or rope, or a 15 mm square net, to a 100 mL
~,l`h<~ cylinder (int~.m~l height after Dlu~ g is 22.5 cm, intr~m~ m~.ter
is 28 mm) co~ ;..g 90 mL of ~ till~l water at 25C. The cylinder is rl~m
in the center, Dlo~ d, and rotated about the center at 8 rpm until ~e sample is
co~ let~ly dissolved in the water.
The agriclllt lr~l formulations of the present invention ~O;~be~DD a number of
advantages over col~ ;o~ grit~lllhlral formnl~tinn~. For ~.~mple, the fibers:
a) reduce worker C~)ODU1~ to potentially h~rmfill active ingredients (e.g.,
pestirirles) relative to coll~ l;o.~ owdcr, ~ mll-, liquid and gel
form~ ti~n~;
b) allow for easy mea~ ent and applir~tion of the proper active
os~ge;
C) ~limin~te runoff from e~cess applic~tinn;
d) provide faster release of the active ;-~ "1;- ..l than f~ed f~s or water-
soluble bags in a mi~c tank;
e) allow for the ~lco~ iull of ;. .~c.~.p~ illc active .. ~ in the same
formnl~tinn;
f) ~.limin ~ os,~l plo~lc".ls associd~d with co-~lo-~ t~A ~&~s of
cc,"~ in~l fom~ tinn~; and
g) in some embo-l;...r.~ , do not cont~min~te a mi~c tank, reduce spray drift,
and target only the locus to be ~ t~d and IL~ ~ reduce waste.
The following P~mrles illnstr~te the present ..l~lti on and are not
Gd as limiting.
FXAl\~PLE 1
P~ )ofaWater-SolubleNetC~ *Met~ lr~ e~hyl
100 Grams of a sGluliGll cont~ini~, 31.S0% ~olyv~ l alcohol (PVA 51-05,
DuPont 131vanol'l9, which has a viSCO~,ily of 5.5 ~ 10-6 Pa s of a 4% a~lue,~,ussolution at 20 C. as (l~tennint~d using the Hoeppler Falling Ball MPthotl, ASTM 1343-56, Part 8, 1958, p 486), 13.5% metsulfuron methyl h~ cide, and 55%water was poured inside the barrels of a twin-cell which was Co~ f ~ d through avalve to a jet ~ 1 spin (JAS) cell of the type ~ oserl in U.S. Patent
Wo 94/23573 216 0 8 ~ 7 PCT/US94/02555
4,963,298. The JAS cell c~nt~in~l (1) a s~ for the e~ctrusion of the
p~lymer sollltion having a capillary di_llct~r of 0.025 cm and an length to
diameter (L/D) ratio of 3.0, and (2) a cull~r~,u~g airjet nozzle having a throatdiameter of 0.318 cm placed co..~-.1. ;c to the ~uln~ for the flow of a high
S velocity air stream. The ~a~ lg b~ cn the tip of the ~ui~ n l and the tip of the
cc,ll~,~ging airjet was mA~ ;nrd at 0.447 cm.
A primary stream of air, heated to 408 C. under a ~l~,s~ul~, of 5.15 ~ 105 Pa
flowed through the ~nnnlns l,e~ n the ~il~nc.~t body and the CO~ lg airjet
and e~ited with a velocity of about 194 m/s. The fibers eAL~udu~g through the
10 ~Illlle.~,l were c~os~d to high vdocity, high t~ rulw~ air for less than one
second, and were partially dried and ~ c~ to low denier fiberæ. A denier iæ
defined aæ the weight in grams of a fiber of 9000 meter length After e~iting theJAS cell the fibers were cA~oæ~,d to a 5CCOn~ stream of high t~,~Ul~
(408 C.) air under a supply ~ Ul~ of 7.22 ~c 105 Pa and flowing through a
L~ibulion plate with 10 holes each having a ~ .. ct~ ~ of 0.102 cm, at a velocity
of 481 m/s and equal to the vdocity of sound in air under the CO~ ;1;O~ of ~e
CA~ 1 The contact time of the fiberæ with the ~con~l~ y high temperature,
high velocity air waæ also less than one second.
The .l;~co~ û~s fiberæ were collected in the form of a bonded net. The
20 bolldulg waæ ~ ed by the ~sidual water in the fiber stream. A ScL~.n;.~g
ele~ micr~ sllowill~; the net is given in Figure 4. The net dL~ol~l~;l in
water in 2 mimltes and had a tensile ~ ,l}l of 0.05 N/m/g/m2.
PXAMP! P 2
A St~LUl~ aqueous scl.~ co..li.;..;..g 30.0% PVA (as used in F ~-..plc 1),
20.0% met~lllfilron methyl h~.bi_idc, 4.5% polyuA~ c binder, and 4S.S%
water was treated as in r;~ c 1.
The net was ~ ~1 using the same ~lucel~ using ~lilll~ air at 428 C.
and scco--fl~y air at 419 C. The ~;A~o~u~e time rem~in~-l the same as in
F~mrle 1. The net dissolved in water in 3 mimltes and had a tensile ~ L of
0.05 N/m/g/m2.
