CA1102692A - Method and composition for the prophylaxis of apple peel spot - Google Patents
Method and composition for the prophylaxis of apple peel spotInfo
- Publication number
- CA1102692A CA1102692A CA284,970A CA284970A CA1102692A CA 1102692 A CA1102692 A CA 1102692A CA 284970 A CA284970 A CA 284970A CA 1102692 A CA1102692 A CA 1102692A
- Authority
- CA
- Canada
- Prior art keywords
- light
- composition
- hydroxy
- apple
- protective agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N3/00—Preservation of plants or parts thereof, e.g. inhibiting evaporation, improvement of the appearance of leaves or protection against physical influences such as UV radiation using chemical compositions; Grafting wax
Abstract
Abstract of the Disclosure This invention relates to a method and a novel composition for the prophylaxis of apple peel spot. Thus one aspect of this invention relates to a composition for the prophylaxis of apple peel spot, particularly "Jonathan" peel spot, characterized by containing at least one light-protective agent optionally along with at least one other biologically active substance, furthermore a carrier, diluent or other auxiliary agent commonly applied in plant-protecting compositions. Another aspect of the invention relates to a process for the prophylaxis of apple peel spot, particularly "Jonathan" peel spot, characterized in that the apple is treated with a composition containing at least one light-protective agent optionally along with at least one other known biologically active substance, furthermore a carrier, diluent or auxiliary agent commonly applied in plant protecting composition.
Description
9~
~ ~` '.rhe invontion rel~te~ to a me-thoe3. and a ~ovel compo~i~tion for the prophyla~:L~ o~ apL:~le pe-3el spot~
The method a~Id compo~ltlon accorelin~ to th~
invention Gan ~be appl~ed to advan-tage on apple~ a.~ :
thin pe~e~l and red~:coloura~ion, such a~ those belong-ing~to the varieties "Jonared"~ "S~arki.ng" and~
most~partlcularly, "Je~nathan"~
:Apple peel spot is a` phy~iolo~lcal di~order /aolour ch~n~e/, l to 15 mm in di~meterj o.~ the frui~t peel doveloped ein the trse or during mainly stora~e owing to~the decompo~ition o~ colouring ~na-:terial,~in:contra~t with:pittln~:~ which means ~mall pot~: al?pearing on the ~urfaco o~ the ~pple and also:
i~iltratlng~; lnto th~ ~pulp. ~ further applo; eli~eas~
caila~ which take~: plaoe duri.:ng the storage o~ -:the: ~ruit~and cause~ b~rowning o~ almost whole part of the pee1.
S~veral chsmical and physlcal methods aro k~owll to prevent apples from peel spotc When tre~Qt:i~g~Qpples:at lea~t ~i~e:times dur1n~ th~ vegetation ~eriod with a spray liquid containin~ o~lcium~ions or oalcium salt~ ~uch a~
~ oaloium~nitrate or calcium chloride/9 a pro-tection ; :~ o~ onl~ ~Q to 30Y~ can be at-~ained, which is insuffi- ; ~ cient:~rom practical~aspect~q , ~: , : ~ :
.
.
, . A 1109-67/EK
. ,.
, . .
: ` :
-~s a ~urther d~E~ad~n:~tage, thl~s treu tmen-t lncreQ~e~
tihe c~l¢lum po~ tate cont~nt o;~ the cel] ~ ~ I t 1 s g~ne-raliy known that ~ ~econdaxy :Eea ture o:~ apple peel ~po~ u~t the accum~lation o~ biv~ t ~atlons g ~uoh a~ calcium lons in the ~3pot~ /Beyer~ E~: The Frul~O Grow. ~, 319~335 /1963/; Schachre~3tAny, Nv ~
Erwerb~obstbau 6, 153-154 /1964/; C3ch.uma~her, R~and `~ankhau~er, P. ~ woi~. Z~ î~ir 0~-t- und ~Yeinbau 102 431-441~ /1966/; Elungarian Pat~nt No~ 159,199tl~
~ hc I~ ae~i~ patent ~peci~ication l~o. 26"
74O descr~ be~ a method ~or p~eventln~ app1e plt~in@; 9 aGaord~ n~ to which the f~i~ i8 treated with al:L
aquoou~ ~olution or ~u~pe~ on cont~ini.n~ a calcium ~alb and ~ ~tvp-~c~1d ¢ompo~itiorl~ The ~top-scald compo~it~o~ contain~ Qn an-tiaxidant ~ ~UCtl a~ dlphen~
~ mlne or 6 othoxy - 15 2-dihydro-2,2,4-tlimethy1quino-l~n~t~ ~he apple~ tre~ted w1th the compo~ition~ aocord-ine to the ~pesificatlon are put 1~to coo11ng t~ks elth~r di~actly ~L~ker the. treatment or ~1fter an i~ter-med~ate stors,g e o~ 5 to 7 day3 at ambient temE)er~ture 4 According to the ~peciflcatiorl the) o¢currenc~ of pitt-lng ~eduoe~ to 2 to ~!8~o in contr~ wlth th~ 55%
ob~erv~d with the aonbro1s.
According to th~ method OI storage under ¢ontrol1~d atmosphere -/CAJ, th~ ~pp1es are ~torecl in
~ ~` '.rhe invontion rel~te~ to a me-thoe3. and a ~ovel compo~i~tion for the prophyla~:L~ o~ apL:~le pe-3el spot~
The method a~Id compo~ltlon accorelin~ to th~
invention Gan ~be appl~ed to advan-tage on apple~ a.~ :
thin pe~e~l and red~:coloura~ion, such a~ those belong-ing~to the varieties "Jonared"~ "S~arki.ng" and~
most~partlcularly, "Je~nathan"~
:Apple peel spot is a` phy~iolo~lcal di~order /aolour ch~n~e/, l to 15 mm in di~meterj o.~ the frui~t peel doveloped ein the trse or during mainly stora~e owing to~the decompo~ition o~ colouring ~na-:terial,~in:contra~t with:pittln~:~ which means ~mall pot~: al?pearing on the ~urfaco o~ the ~pple and also:
i~iltratlng~; lnto th~ ~pulp. ~ further applo; eli~eas~
caila~ which take~: plaoe duri.:ng the storage o~ -:the: ~ruit~and cause~ b~rowning o~ almost whole part of the pee1.
S~veral chsmical and physlcal methods aro k~owll to prevent apples from peel spotc When tre~Qt:i~g~Qpples:at lea~t ~i~e:times dur1n~ th~ vegetation ~eriod with a spray liquid containin~ o~lcium~ions or oalcium salt~ ~uch a~
~ oaloium~nitrate or calcium chloride/9 a pro-tection ; :~ o~ onl~ ~Q to 30Y~ can be at-~ained, which is insuffi- ; ~ cient:~rom practical~aspect~q , ~: , : ~ :
.
.
, . A 1109-67/EK
. ,.
, . .
: ` :
-~s a ~urther d~E~ad~n:~tage, thl~s treu tmen-t lncreQ~e~
tihe c~l¢lum po~ tate cont~nt o;~ the cel] ~ ~ I t 1 s g~ne-raliy known that ~ ~econdaxy :Eea ture o:~ apple peel ~po~ u~t the accum~lation o~ biv~ t ~atlons g ~uoh a~ calcium lons in the ~3pot~ /Beyer~ E~: The Frul~O Grow. ~, 319~335 /1963/; Schachre~3tAny, Nv ~
Erwerb~obstbau 6, 153-154 /1964/; C3ch.uma~her, R~and `~ankhau~er, P. ~ woi~. Z~ î~ir 0~-t- und ~Yeinbau 102 431-441~ /1966/; Elungarian Pat~nt No~ 159,199tl~
~ hc I~ ae~i~ patent ~peci~ication l~o. 26"
74O descr~ be~ a method ~or p~eventln~ app1e plt~in@; 9 aGaord~ n~ to which the f~i~ i8 treated with al:L
aquoou~ ~olution or ~u~pe~ on cont~ini.n~ a calcium ~alb and ~ ~tvp-~c~1d ¢ompo~itiorl~ The ~top-scald compo~it~o~ contain~ Qn an-tiaxidant ~ ~UCtl a~ dlphen~
~ mlne or 6 othoxy - 15 2-dihydro-2,2,4-tlimethy1quino-l~n~t~ ~he apple~ tre~ted w1th the compo~ition~ aocord-ine to the ~pesificatlon are put 1~to coo11ng t~ks elth~r di~actly ~L~ker the. treatment or ~1fter an i~ter-med~ate stors,g e o~ 5 to 7 day3 at ambient temE)er~ture 4 According to the ~peciflcatiorl the) o¢currenc~ of pitt-lng ~eduoe~ to 2 to ~!8~o in contr~ wlth th~ 55%
ob~erv~d with the aonbro1s.
According to th~ method OI storage under ¢ontrol1~d atmosphere -/CAJ, th~ ~pp1es are ~torecl in
2~
an atmosphere of steady oxygen-carbon dioxide ratio. A disadvantage of this method is that the volatile substances enhancing ripening and other meta-bolites (carbon dioxide, ethylene, etc.) formed during storage must be removed. The installation of such a cooling store equipped with ventilation and other instruments is rather expensive and greatly increases the costs of the fruit. Another, more serious disadvantage of this method is that when removing the fruit -from the store it begins to spot rapidly, and becomes very spotty when it reaches the market (Smoch, P.M. and Blanpied, G.D.: Proc.Am.
Soc. Hort. Sci. 73-77 /1965/).
The invention aims at the elaboration of a novel method and a novel composition which enables one to prevent apple peel spot more effectively and more simply than the hitherto known ones.
According to the invention there is provided a composition for the prophylaxis of apple peel spot which comprises at least one light-protective agent together with a carrier, diluent or other auxiliary agent useful in plant-protecting compositions and at least one other biologically active substance. !
According to a preferred embodiment of the invention there is provided a composition for the prophylaxis of "Jonathan" peel spot, which contains 0.05 to 99.5% by weight of at least one UV-absorber together with a carrier, diluent or other auxiliary agent useful in plant-protecting com-positions and at least one other biologically active substance.
r~
6~;~
'rhe inven~ion i~ b~ed on the recognitlon ~hat when ~ppleæ are treated with Q compo~3itlorl containing at least one llght~proteot~v~ agent" pee~ ~pot c~n b~3 elin~inated comple tely or at lea~ t reduced to the mini mum, - q'he ma:Ln ad~a~ta~e OI the proce~ ~nd composi-- tion accordin~; to the l~ventlon over th~ known O:tle9 -i~ -th0,t evon a ~in~le tre~tmeIlt i~ geIlerall~r ~ufficl-en~ to prevexlt peel ~pot prao ~ically comple~elyO
I t i~ lmport~nt ln th~ large-~cY,le hor ticulture ~ but e~r;on.~or ~mall-p~:rcel owner~ th~t only a ~l.ngle 3pray treatment is required:instead o~ e,g, f:~vo treatmontsO
A ~urther advantage of the method and ¢omposi~ion acoording ~o the invention ia that the apples are p~eserved even a~t~r ~tora~e in ~he wlnter season~ that ls they ha~e a lasting re~ult in con~ra~t to the C~-~tora~e methodO ~oreover, the ~rult pulp doe~ not ~o~t-~en a~ after the~ -ray treatment. Another signi~icant ~dvantag~ i~ that ~h~ novel method of ~he in~entton .
doe~ not rcqulre ~y ~p~cial~in~tallatlon ~n~ equlpment~
~1nee th~ spraying device~ alre~dy ln use ~n be Qp-plied~ It should be mentionod a~ a specific ~d~nta~e - that the oral to~i¢ity o~ ~h~ u~ual li~ht-protect~ve ~erlts is very 1 OW9 i E~ any., .~ , .
~ 6 ~
; The light-proSeotive agents applied ~n the method and composition of the invention are known compounds~ Some o~ them are applied :Ln the plaætic :induætry aæ IJV ~tabili~eræ, whereas other~ in the ~ield of coæmetic~
On the basis o* their fu~cti.on~ the light-protective ~ent~ oan be classifle~ e.g. ~ ~ollows:
light screeners, UV absorberæ, qUenCher9 ?
radic~l sca~engers, and perox-ide d~co~posers~
IIo~veverg i~ is more appropriate to cla~si~y the lit~ht~protective agent~ ~ccording to their chemLc~l - struc-~ures~ since a lit~ht-protective agen-t may have more -than one ~uno-tion.
The l.i~ht-pxo-tective agents; i~e. tlle active agen-ts o* the co~position~ accordin~ to the in~ntion can be selected e~g~ ~rom the following oompound typeæ:
benzophenoneæ, benzotriazoles9 dibenzot,riazoleæ~ tri-tri~Y,olobenzene derivatives~ aromatic estern~ substi-tuted acrylonitriles 7 met~lorg~nic compolmds, alic~clic - dienone derivatives9 furthermore certain inor~anic pi~-ments~ etc~ The compositions accordJn~ to ths inven-tion may ~lso contaln more than one ligh-t-prot.ective agent~ ~nd they may belong to -the ~ame or dif~ere~t chemical groups~, Thus, the inve~tion relates to ~ proce~ for the prophylaxis o~ apple peel ~pot, p~rticularl~ peel ~pot of ~pple~ of "Jon~than" v~rlet~ characterlzed in that the apple i~ treated wit~ E~ compo~ition conta~n-ing ~t least one li~ht-protective ~gent, optiQnally at least one other known blologic~lly activ~ sub~tance ~nd optiona]ly one or more car:rier, diluent and/ or auxiliary Elgent common.ly applied i~l ~uch composition3.
Furthermore, the invention relates to a novel compo~i-tion which contains at least one light-prot~tive agent, optionally along with at ~east one other known biolo~ic~lly acti~ sub~tance and with a carrier ~bind-ing agent and/ or auxiliary agent commonly applied in ~uch compo~ition~.
Accordin~ to the method of the invention the novel composition, preferably in diluted form, is ap-plled on~o the apples pref~rably on the tree, iOe.
baIore harve~t, but one may also treat the ~pple~ alre~dy har~re~ted .
In accordance with the invention e.g. the following benzophenone deri~atlves can be appllad :
2, 4 - dihydro~yberlzophenone, 2-hydro~y-4-metho~ybenæophe~one~
;26~2 ~, 2 ' -dihydro~y-4, 4 ~ ~d~..methoxybs-3næoplleIlons~, 2 9 2 1~ ~ 4 5 4 ~ -te trahydro~ybenzophenone 2~hydro~y-4methoxybenzopheno.ne-5-~u.L:Eonic acid~
~odium 2-hydro~y-4-methox.ybenzophenone-5-sul~onat~, Z~-hydroxy~4~metho.xy-4'-methy Lb~nzophe~one, 2,2;'-dlhydro~y-4-methoxybenzophe~Qne, 2-hydroxy-4-n-heptoxybenæophenolle, 2-hydroxy~4-n-oc-tyloxybenzophenone~
2-hydroxy-~-metho~y-2'-carbo$ybenæophenone, Z-hydro~y-4-dodecylox~benæophenone, 2~27-dihydroxy-4,4.'-dimethoxyben7lophenone-5-sulfonic . ~
acid, and : : :
2-hydroxy-2'-chlorobenzophenone.
Particularly pre~erred members o~ the ben~o~
phenone derivatives a:r e the following one~:
2-hydro~cy-4-n~octylo:~:ybenzophenone~ ~.
2-hydroxy-4-n-heptyloxybenzophs~ns)ne"
2-hydroxy-4-dodecyloxybenzophenone 2,2 ~`~7 4~4'-tetrahydroæybenzophenone, ~nd 2727-dihydroxy-4,4'-dimetho~ybenæophenone-5-sulfonic aoid~ ~
~: : , In accordance with the :invention e.~. the ~ollowillg bs-3nzot~rlazole and dibenzotriazole delivative~
, .. . . . . . . .
6~2 `.
p~l~ed:
Z-/2'~hydroxy-5'-Methylphellyl-~-berL7otri~zole, 2-/2'-~lydro~xy-5'_n-oDtylph~nyl~-~e~Lzotriazole9 2-/2'-h~droxy-3'-tert.buty~-59-metllylp~onyl/-5-chlorob~nzotriazole;
~2-/2'-hydro~y-3 9 5~-di-~ert~butylphenyl/-5-cllloro-~ ~bonzotr~azole, ~nd : ~
: 5~111I-5~,1l'-dldehydxobe~zotri~zolo L?'9l-af~bénzo-; triazole~ .
Particularly pxe~erred member~ o~ the benzo-tri~zole ~erlva~ive~ are the ~ollowing compounds:~
2-/2'-hydroxy-5'-n-octylphe~yl-/benzotriuzole9 ~2-/2'-h~droxy-3'-te~t.butyl-5'-m~hylphenyl/-5-ohl:or.o~eD~o-triazole~
Z~ 2'~hydrox~-3',5~'-di-tert.butylphenyli-5-ohloro-~
~benzotriazole, and 5,11I~-5',11'~did0hydro-benzotri~zolo`L29 ,l-a ~benzo-tria~ole~
`In accordanoe with:the i~vention e.g. the llowi~&^ tri-triazolobenæene~deriv~tives can b~ :
- ~applied~
;~2,~,8-tri/ph:enyl/-tri-~-triazolo/a~c,e~ b~1lzene, . :
:: :
, ;
- . . ., ~
~ 1~) 2,5,8-tri/n1trophengl~tri-~triazolo ~a~c~ enzene 2~5,~-trifdinltrophe~yl/-trl-~-triazolo /a,o 9 ~/benzene In accorda~ce with ~he ^ln~ention e.g~ ~h~
followl~ aromatic estarn c~n be app~ied~
digalloyl tr~ol~at~
ph~nyl salioylate 9 ~ `
p-octylphenyl ~alicylate9 t~rt~bu-tylphe~yl ~alloyl~te, resorclne monobenzoate, and 2,~4-di-t~ert.bub~lph~n~l 3,5-~dl-t~rt.b`u~yl 4-hydroxy-be~n~oa~e.
Pre~erred repr~entatiro~ of th~ aromati¢
~ te~ de~i~ati~ea are th~ followi~g~ompound~:
dig~ o~l t~ioleate, p-oct~lphenyl ~alicylate, re~or~inol monobenzoate, and ~ 2,4-di-tert.butylphe~yl 355-di-tert butJl-4-h~dro~y-~i~ ~ be~nzo~te~o In ~c~ordance with ~the invention e~gO th~
~ollo~i~g ~u~titut~d a~rylo~itrile der~vativ0~ ¢~n be ~applied:
eth~l~ diphenyl~acrylonitrilat~
2-ethyl-~e~l 1,19 d~henyl-acrylo~i~rilateJ
meth~ oyano-~ -m~thyl-4-methoxycinnamabe.
.
z Pre~rr~d r~pre~erltatives ~f th~ ~ubsti~uted acrylonitrile deriv~tlve~ are the ~ollowIng compounds~
eth~ diphenyl-acrylQnltrilRte~
2-ethylhexyl l,l~ diphe~yl-acrylonit:rilate~ and methyl~ -cy~no-~ -m~thyl-4~metho~ycinrlamata~
In accordsnce wlth the ~nve~icn e.g~ tha ~ollowing metalQr~anic compound~ c~n bo ~pplied: :
~2 9 2'-thiobi~/4-tert~octy].pheno.Late~ - n-butylamine nickel /II/, ~
B nlckel bi~octylphenyl ~ulf~d.e /~erro ~ lOl and A~ 106 ~ 9 nickel dibutyldlthiocarbamateg f3,5-dl-tert,-butyl~4~hydroxyben2yl~pho~phorio acid mono0thyl~ster 2:l nickel chela~ei Irga~tab ~002, cobalt /II/ di~yolohexyl-dithiopho~phinateO
Pr~ferred member~ o~ the met~lorganic com-pounds are ~ ~ol~LQws:
/2,2~-thiobi~/4-terb~octylphenolQ-te/ -n-butylQmine-ni~:el /II/, and nickel~hi~oc^tylphenyl ~ul*i.de /~erro AM lOl and : Ferro ~-105 /.:
Of the alic~clIc dienone derlvative~ 5~/3~3 dimsthyl~norbQrnylidene/-3-pentene-~-o~e c~n be ~p~
pli~d to ~reat advantago.
/ r~ lc In accordance with ~he in~rentlon ~g~ tha follow:~.n~ inorg~lic pigm~nt~ can ~0 appliads c~bc~n black, tit~n~um dio2ide, and ~in~ o~ ide O
Particularly pre:l~erre& member~ of ~ho i~organic pi.~;m~nt.~ are e.~;~ t-ltanlum divxide and zinc ox:lde.
The me th.od of ~he inv~ntlon al~o permit~ tho u~e o:~ compo~i t:i on~ wh~oh cont~in~ more than one ll~ht-..
protective a~nt99 ~uoh a~ one or more b~nzopheno~eand/or one or more benz~tr~a~ol~ ~ndfor on~o~r mvre ~:lbenzotriazole~andtor one~ or moro t~iæ-tria&oloberl~e~e : deriv~Lti~re~ axLdtox~ one or mor~ aromat-l¢ e~erJ~i and/Qr -~o ~e or more ~ubstituted acrylonitrile ~nd/or one or more metalor~anic compou~d/~/ ~nd/or orl~ or mor~ aliph~
- . , Rtio dienorle derivative/~/ a~d/or one~or more l~orga~i¢
: pigment/s/.
:~ :
Thes~ composi-tions ~cGordi~:Lg to th~ inv~ntion - -oontaining more than orle: ligh~-proteotlv~e agent~ m~y contain e~g. th~ ~ollowin~; ~ombi~aation~ o~ active :
~gents:
2-/2 ? -hydroxy-3 ~ -tert .,butyl-5 '-me~hylphenyl~-5-,chloroben~o triazo le and 2-/2'-hydro~y-33,5' di-tert.
bu~ylphenyl/ ~5-ahlorobenzotrlazole, zinc oxide and 2-/23-hydroxy-39-te~t.but~;5'~methy1 phenyl/-5-chlorobenæotriazole, -~ L~ -292'g~41--t~tr~hyd~oxy~erlæo~herlono and 2-hydro~y~4-methoxyb~nzophenvrle~5~sulfonic aci.cl, 2~ethyl-he~rl 1,l7- diphonyl~acrylonitril~te ~nd 2 h~droxy~4~m~thox~benzophenone~
5-33 9 3-d~me-th,yl-2-norborn~l~d~ne/-3~pentene-2 one ~nd Z-hydro~y~4-n~oc-tyloxybe~nzoph~none 9 2-hydroxy-4~n-o~,tylo~y~enzopll~none and 2 /3'-tert.
butyl~27-hydro~y~57-methylphen~l3~5-chlorobenzo~
~riaæole, 5~/3~3-dime-thyl-2-norbornylidenej-3-pentene-2-one d ælnc o~.ide~
-/313-dimethyl~2-nor~ornylidene/~3-pentene-2-ono and ~.ig~lloyl triole~-te~
2-ethyl-~e~yl l,17-dip.henyl--acrylonitrilate and 2-hy~roxy~ n~oc t~loJ~ybenzophenone ~
2-hydro1ly~4~ oG-tyloxy~ 3n ~;ophenone 9 2~f3~ ~ert O
buty1-29-hydro~y-5'-me~hylphe~yl~-5~chlorobenzo~ri-a~ole ancl 5-~3 7 3-dimethyl-~norbornylidene/-3-pen~en~-_~-one, 5-J3 9 3 dimethyl~2-~lo~bornylid@ne/-3--pentene-2~one ~nd nicke~ blsoct~lphen~l s~lfide /~erro AM-101 ~Z-/2:'-hydroxy-3~5'-d~--tert~bu-tylphenylf~5-chloro-~enzo~riazole ~nd ni~kel b~soctyl phenylsul.~ide ~e~ro AM 105~ 9 2;r~2)-hydro~-37~5~,~di-~er~Obutylp7lenyl/-5-chloro-~ 2~Z
- 14 ~
ben~otrlazole a~d~/2~2~- ~hiobi~ n-octylphenolat~/
-n-bu~lamine n~okel /II/ 9 2-e~hyl~hexyl l~l' diphen~l-aox~lonitrllate and ~2925-thiobi~4-tert~octylphcnol~e/-~-but.yla~ine-nickel j~ abc~
should be ~tre~sed9 howe~er, that:the abo~
li~t~ ~f li~ht-proteoti~re agen~æ and combination~
are not e~haus~i~e~ ~ince other light protec~i~e agent~ ~nd combinatlon.~ ca~ ~lso be ~pp~ied~in~the method ~nd composition a¢cording to the inve~tio~
Th0 above li~t~:~e~e merffly ~o lllu~trate ~he~in-v~nt~on.
:
: : The light-proteotive ag~nt~ themselves~o~
; ~th~ir mlxtu~es are Gonverted ~i~to compositlon~ ~nd the`:re~ult~ ¢omposition~are ~pplied ~ a~ent~
~or the preventlo~l o~ apple pRel~spot.
. The ligh~-protective agents themsel~e~ or their mlxtures c~n be converted into conventional -~oompo~ ion~ such a~ wet~able spray powder~ /WP/~
lowable ooncentrateæ /particularl~v water-~oluble .
p~wder ¢onc~entrabes, wate~-soluble~sol~tion concentr~
:~ ~ te~ ~WSC/~ emulsi~ya~le~ concentra~es /E~/ or compos:i-: tion~suitable for ultra-low-volume /ULV~ ~pp~ica-tio~, $he cQmposit~ons ~re prepared accord~n~ to woll-kn~wn methods, e.g. b~ ~dmixin~ the light-pr~-, .
, tentiv0 ~ or ~i:~tull~e~ th~r~oll:' with l~erl;~ 2~01~ld os~ r~ D ~ U0~ I' oth~r a~ 0 ~o b~ ~ 0~ ~k~ 3~ t~i~S~ p~
~d d,~p~B~g ~ o ~ $r~ 9 ~nt~c~
~dh~3~ n~ g~ p~ a~ or ~a~tai~ial~ o:~ improvl~g the b~ logllo~l a~ti~r:Lty9 Q~ti~-3Lm~ s p A ~ol~d ~ri~lDr3 or d:Llu~Ilt~ ~" g~ th~ ~ollow--i~ subs~t~ oa~ b~ appl~d s ~e~r~ ts~ral and ~s~the~l~
~illoats3~ p 3:i.1il.0~ s a;:ld~ ox~ ~odi~lecl clay m~ ral~ and b E3nto:~i t~ c~ ar~o~t phO8phat;1El~;p 0ti8~" e~gO dlatom;~Lo~ou~ carlth~ d~lo~ teg oal~c~
~ag~ m o~fl~ ç
: ~ O:f ~he lls~ d oarrie~ dilu~ d ~l~e~lts 0O~0 w~4ter" C~rga~io 901~eI1~3 a~ld tll~ tUrel~i ~hereo~ Ot7L
a~3 alos>hol~3 ~ e.~ tha~93. ~:~d e~ha~l eto~ ) ~, glyoo3.s .
(21UOh a~ ~ly~erinE3 ~tc~ t~n-3~3 Cs3aLch a~ d~me~hyl keto~e~
m~t~yl~ethyl~ to~ o,, ) ~ e~tor~ ~ ~uoh ~s e~llyl acetateg ~_ ~d ~obutytao~tat~, amyl aoe~a~a eto,, )~ laotone3 ~suoh a3 ~butyrolacto~e et~ ) 9 la~t~ms ( r3uch a~ amino capr~ -~) la~ 3 ~o~ d~ g ~u~h a~ ma~h~r7 ~rm~ d ~ . 3 al~p~ÆLtlo; oaclic a3~d aroma~c ~r~6~ax~bo33~, arom~tlo-~al~phat~ h~rclrocar~o~s ~auch ;E~3 h~3ptane, he~a~e9 cyolo~
he~ e, :~ylen~, tolue e e~c, ~ ~d th~ ~;c)lv~tl!3 de~i~ated wi~ shell~ol9 No~a~ol et~, oan b0 m~ntio~led.
The w~3t~:~g~ ~ls~ 1~,e and ~m~ Ey:lO~g ae~$~39 i')1arl~
~` 16 ~
~dhe~3i~e~ c?~lc:L~ a~d a~t;~ t:lLok~ enlta oatl l~e o~ lonio alld ~oll_il o~in o~arQOtar~ The ~ub~ta~oea o~
~o~1o ohar~ter o~ lbe aalio~ s, oatioll:Lo a~ amphot0I~.
~he ~o~io ~ t~oç~ h~ ~Ql~ ar~ ~o 11 ~s~tio~led s 3ul~a~e~ ~d ~:he1r ~alts S, sul~o~at~ a~
~heir ~alt~ oh as laur~l ~ulfa~e~ a~d lt~ ~alt~, be~:~e3ul~0~ate~3 a~d their ~alt~ petroleu~sulfo~ate~
a~nd their salts, soap~ e.~0 :3odilam ~o~r~t~, e~oO
0~ ths~ ~o~_io3~io ~ubJ~anoe~ e,g" the ~ollowi~g ar~ to be me~t~ o~ed ~ blook polyaler~ t~f etb~y~e~Leo:~ide a~d E~opyl0n00æ~d ~d t~eir ~ter~ or e~hers a~d the a:latural or lly~'chutlo oli~oro~oleou:Lnr ~ub~lb~roe~;.
~ .17 ~
Wettable ~pr~r powdsr~ can be pr~pared e.~ .
by ~srindi~ the ~olid light-proteotive agent/~/ ~nd the o~her au3 :iliary ag~xlt/~ ? ~ur~actaIlt/~J a~ld:
, a~ t~/ fo~ main~ainin~; or ino~e~in~ th~ blolo~ical ~aot~ by ~o a particle ~ize o~ preI~r~bly below~100/um~, p~rt~ular:L~ bolo~r 25/um.~ and homogeni~in~; ths ~ro~nd ~hstQn¢e~- ~ Wlth llquid ~f~ct~t~, on~ oan 8190.
proceed by applyin~ the liquid surfaotan~ /e.g. by a~omiæing j onto th~ ~olid or~;anic or min~ra~. diluo~t~
or onto ~he powder~ m~:ctur~, p~o~erably below lOO,!,um., :
.
part:iGularly below 25~ n pa~ticle ~iæe~ al~eady~
: c~ntaining~th~ æolid light-prote~tlve agent/s/.~ :
A a~i~ilar prooedure o~ be appli~d ~ith liquid li~h~
pro~eo~tl~e age~t/~ ettQbl~ ~pray:powder~oan al~o -`
be prepared by homogeniz~g:~-the ~round component~
oompr~in~ th~ homo~eneous ml~ture e~OE. on a roll~r ~mill, and then grinding -the compres0ed substance ~o th~ par~ioIe ~lze give~ abo~e.
Water-~oluble powde~y conc~ntrate~ can ~e pr~p:ar~d e.~0 bD grindin~the solid water-soluble proteG~ive agent~ , solid sur~aotant~/ and other zolid add~t~ve/sJ ~eparate~, and homogenlz~n~
h~ ground sub~ta~oe~ When liquid surf~ctant~ are : ~
~pplie~9 one ~an also proceed by ~u~pendin~ t~he pre ~iou~ly ground solid compDnents ~n ~n organi~ ~ol~ent 6~;~
.
oont~ining o~e~ or more li~id ~uriea~ba~t~u/ 7 ol~d l~hen :dr~in~; th~ ~u~p~ o~ e.~5. bJ ~prayin~ ~, In this w~r ur~ta~ pl~ea orlto th~ ~3U:rI QCe of ~e~
ol~id~llght-prot~ re~a~ ~d~the ~ d d~lu~nt.
ul~i~yable~ ~o~rloèntra~e~ a/ ~appl~c~
~f~r ~he prQ~ràtlcin ~o~ di~pers~bl~ OU~3~Bp~l àmul~ions ~an~ be pr~pa2~d by ~di~s~l~ring :~on or ~ re it~ro~o~v~ sg~n1i~ and ~s ~r~ em~
ing~a~ér~t Qa ~finéd~abo~e in a wa~ olble ~olverlt. The re~ultin~ emulsi~yable~ ~uon~tra~t~
emul~lon:with wa~er ~i~hor sp~ ou~y or upon; a llght m~ohan~oal i~bex~entl~ ~d th~ ~r~ul$~
liq~d~ ~uls~0n~0~n be ~1~orea :~r: i~::prolo~d~
per~~o:
Water-~olubl~ ~liquia~Go~eI~r~ $~ ca~
be ~a~;red ~y d~s~ol~ ; t he l~ prot:eoti~age~
d ~tha appropriate-w~ter-~olubl~ a:~r a~en~
in w~e~: a.nd/~r in ~ wa~;er-ml~cible ~olve~t. :~A sp:~y .o~u~tion o~ the desi~ed ~onoent:~lon c~ b~ pr3par~d by~ d~lution ~ith~water~
ith~appropri~te ~amul~ifyi7~ a~en~ on-rtr~ted-~qu~ou~ ~olutlon o:~ ~h~e ~l~t-Prot~stiYa .t ~ o-:be~ përaed in:~a wa~ o~le~;
lquid~ t~ p~epare l~er~a emul~ion~ hu~ he oper ~sol~tlon~ of th~ ~so~ven~s ~d ~ aet~C~, ..
- . ~
- 19 ~ 6~Z
light-protectlve compo~ition~ ~ppl~ca~le in bhe ~
~ulture for ~he prophylaxi~ o$ ~plpl~ p~el ~pob c~n ~be pr~pared5 wh~ ch compo~itio:n~g whe~ admixed with -wat~r or a~w.at~r-lmmi~e~lble llquid~ ~o~m dl~per3~ :
ey~tem~ /ev~n mol~culBr dlsper~on~ able ~or~pro-longed:perlod~
: ~ Spray ~olution~ oan be prepar~d:in -B kno ma~n~r b~ dil~ g ~he light-prot~at:i~e~cQmpo~itio~a:~
:
w-~th ;tYatar~ ~he ~pray ~olution~ contain the li~ht-:
-p~o~ective agéntfst ~o~erally in an ~mou~t~lower th~n 5 % b~ weight~ p~r~icularl~ ln~n Qmount of l:to~
0.1 a~o by wel~h-b. One o~n;al~o:proc~ffd;by:.~irst pre--parlng ~pray~liquid~ which ~on:~ain only a~:3in~1e light-proteotiva~aee~t, and th~n poolin~ ~he~e 11-qu.ld~ ~e~ore u~e O
he compositi~-n~3 aoco~rding to the invèntion~
w~r~ :screen~ by :u~in~ ~p~aD li~ids a~ describè~
abc~e~; E~ch o:e the compositions were ~est~d g~ne~
ally on l~O ~pple~ ~a~ follows~ ~ thg applé~ ~werè im-mer~ed into about ~ 1~ o f a~ ~pray liqllid, r~mo~ed ~a~t~r ~b~ut 1~ mlnu-te, allowed ~Q dr~, and then irr~dl-sted ~ur:Eth~ a ~Tu~gsram 11 Ge~nlcid ~F" type ~ meroury l~mp /wàv~leng:th r~g~O 1~5 -to 578: ~ Erom ~ d~tance OI
~4~0~: cm~Dependi~g on their colour~nt ¢ontent~, t!he `~
appl~~ were i~radiated for 1 to 5 houre; the ~o~e-b ~r r~le ~la~K
~0 ~ ~ 6 cololl:red a~)pl(?~ w~x~e ,~ner& 11y i.rrad lated fo:r f~hort-l Q:r ti.rnes ~ rrh~ lrracli~ l;ed Flp~le~ alld the non ~irra(~iat-ed ones 3er~illg ~S coni;rol~ were .s tored for 2 morlth3 at 4(~ and tl!len the rc~u Lt~q were ~v~lunted. q`he spo t1 on t~Ic i rrad~ ed ~ides of the applc~ a~pcar ~mul-tarl~ou~;ly with the na-tural peel spo-lis~ consecluerltly ~h~ ~o~re ~cre~n:ing method i~ in~-~irm co:rr~lation with Lhe :Eie:Ld oxp~ri.ments.
:~n -the -Pie:l.d e~pex irnoIl-t~ the ~pple tree~
wer~ sprayed sorne weelcs /pre:~erably 3-to 6 weekG/ :be~ ~ -l~o:r e harvQ.s li . Depend.irlg on !ih~ stren~; th of sun~hine the trees w~?re ~prayed onc,e or tWiC~?- GeIl~raIly e~en ::
one ~pl!~ayin~ p:ro~ides ~go(~d r~sults. When there is .
st~oll~r sunshin~ dur:intg r:Lper~ g, i t: is pre~erred to use ~a ~pray liquid wi-th iIloreas~d UV absorber con-~cen-trat:ion .in orc~er -~.o eliminat,e thc~ need OI double sprayin~r~
1~ well~proved teclmique o-~ spray in~; accor~ing to th~ in~ tion is the soaking me~thod.l This m~thod requires 2 ~o 10 li-tres, preferabl~r 3 to 7 litres ~OI
~pray liquid per~be~rer un~i.t~ ~he tern~ ~Ibearer unit"
refer~ to the ylelding area /re~ard~Less v:E t;he sub~
jec-t ~ varie ty ~nd ar~e / which can b~ sprayed in a~ ;
~ingle spraying~ with 15 lo o-.E l~quid, takin~; into account th~ spray~n~; efPic:iency OI ~ ba t~ery spraying ~;P2~i~2 - 2i ~nachino with 1~ 5 mrn~ n~zzle bores a~ 8 atml, ln~tlal-pressur~ /Agr-lcultural I-exicon/ MQZ~ga~daSa~;~ Le~
kon~ NlezQgazdasagi Klado, Budapest, 1958; Vol. II, P~ 593./ 7 The in~Tention i~ elucidated irl dat~il by: the aid o~ the f ollowing non;~l~mil;iIlg Ex~le~"
x a m p ^1 e ~ .
2 9 ~-DihydroxybenzQphenone /par~icle s~ze ~low lG/u~
Highly di~per~e ~lc1¢ acid /Ultra~
Aero~il, DurosilJ ~3 %
EQoli~ 42` %
~HOE 8 1880 /Ho~ohst; ~odiu~ salt o~ an sliphatic sul-f onic ~¢ld~
HOE S 1998 /Eo~c~t; f~tty alcohol~poly~
4.% ~.;
glycoleth~r e lQ~
2~2~-Dihydrox~-4j4~-dim0thoxybenzophenone /paYticle size: b~low 10/um/0 ~ 20 %
Highl~ disper~ ~ilicic acid ~Ultra~
~eros1lq Durosil/ ~ 35 %
Kaoline ~35 %
Tri~on ~-100 /~ohm a~d lIaas; octylph~nol~
~r~ C
Z~32 , poly~l~col.ethcr~ 5 ~o Sodium lauryl~ulate 4 %
Pol~vi ~ lpyrrolidone K gO /GAF Corp~
~00 %
Exa~ple ~
5,11H-5'~ ideh~roben~o~ria~olo-~9 71- ~benzotriaæole /pàrt~cle.~ize~ below 20/um-J . ~ ~ %i Kaoline ~o~ %
Silioa gel o~ great ~urface area ~5 %
~onylphenol-polyglyool~her /E0 ~15 / 4 %~
Polyvi~ylpyrr~lidone K-90 /GAF ~orp./
:' 100 ,~
2~/2 ? -Hydro~y-3'-tert~but~1-5~-meth~lph~nyl~--5-ohlorobenzotrlazo~ /particle ~ize: be~
low 20~.um~t ~ 45 %
2-/2~Hydroxy-3',5'-di-~er-t~butylphenylJ~
-chlorobenzotriaole~/p~rt~cl:e siz~e: below ~ :
}O~um.~/ ` 40:% ;`
: Siliea gel o~ ~xe~t ~ur~ce ar~a ~ lO ~o Nonylphenol-polyglyooleth~r /E0 15~ 4 %
Poly~inylpyrrolidone K~90 ~GA~ Corp.t 1 ~
100 %
:~ , m~
Zlnc o~lde Jpa~ticle ~ eO ~ 5~um~/ 90 %
Ga~a~ ~M-710 /G~F Corp./ 2 %
Tri~thanolamin~ l %
Silica ~rel o~f ~roat ~u~face arQa /Aero~
~uroqil~ Sup~rsil, etc/ 5 %
Poly~inylpyrrolldone ~-90 /G~F Sorp~/ ~
100 %
~no o~icle /par-t~cle size~ below 5~um./ 60 ~o 2-/2~-~Iydroxy 3~-tert.butyl-5t-me~hyl~
phen~ 5-chlorobensotrlazole~ ~ . 25~%
Sil~o~ gel o-~ g~at ~ur~oe area ~Aero~
Durosi]., Supersi~/ ~ 5- %
001-.~lph~nol-poly~lyc~le:the~ ~0 lO~ :6~%
E-kha~olamlne ~al~ o~ Ga:fac RM-lO /~' Corpc/ 3 %
Roly~inylpyrrolidonQv K~90 JG~' Corp./ ~ ~
100~ % .
~ . .
2~Hydro~y-4 mcthoxyben~ophenono-5 ~ul~oni~
.
acld ~ ~ ~ 7-5 %
Sodiwm c~rbo~ata 81~ 20 ~%~
Sod~um d~oc tylul:Eo~u~c~at~ ~2 ,$~%
Pol~vlnylpyrrolidone K~90 fGAF Corp~
lOOoO %
~sl~ rl~ !
.
z ~ 4 2 1l 2 '~DihydroE~-4, 4 ~-dimetho~:yben~ophenone-~5-~U1fOniC aCid ~Od1~ a1t 90 %:
SOd~ diO~tY1~U~ UO~in~t~ 5 ,S
PC 1~1nY1PY~rrO1idOne K-90 -J~F Corp~
~0~ ~ .
2~, 2 ~ ihydroxy~~ dim~tho~ybenæophexlo~e- : :
-5~-~ul~Qnlo ac~d ~odium ~a] ~ 90 Sodium ~i meth~l~ol~ taurimide 5 ~HyarQxy~th~rl cellulo~e~
, ~
2~Hydrox~-4-methoxybenzophe~one-5-~ul~
~onic ~-cld~ ` 75 ~%
: Sodi.um carbo~at~ . ` 20 %
Sodlum d~oc ~ylæul:Eo~llc¢lnate 100 %~
Hydrox~4-metho~ybenzoph~none-5-~ul-:
- :E'o~i~ ~old ~ 2 ~;0 -Tri~ thanolamine ~ ~ g.- .
. Ga~ç R~a-510 /GA~ Co:rp./ ,5 ~
Ethanol 5~9 ml~.
W~l;ex: _l ml.
10 mld, - 2~ --~,~ "
2,~'j4f4~T~trah~dro.~nz~phen~ne 005 ~.
Z~~Iy~ 4-m~th~ ~n~h~none-5-~ul~oni.~
cid . ~ 5 g.
l'r.iebh~lam~e 0,75 ~faIac ~~ p ~,Yo~p~/
Methano~ ~ ml~
Wa~er l,ml~_ ~ lO.O~mlO
2 ? 2~4j~-Tet~ah~oxyb~zopheno~e~ Z ~.
h~olam~n~
~P~l~o~yethy~ or~i~ane-mo~op~lmit~e~ ~ ~ 2 g.
~t~hanol 10.0 ml~
2-Hydroxy-4 m~thox~benæoph~non~-5~ul*onlc :
: a~
O
9~'~ 4~-Te~rahyd~o~benzQphenone l:g~:
~ rie~anolamin~ ~ 0~5 g~
`~ rolyoxy~thyl~n~-sorb~ban~-monopalm~.t~te 0~5 g.
'510 /GAF Gr3?~ -5 B~
hanolami~e monoQl~a~e O 0 5 ,g., -opropanol 1 ml .
, , .
~ 6 _ 2 Me~hanol .
: N.0 m~.
~h~ oompo~ition ~o~m~ ~ oollo~dal ~olu~io~ ~it~ w~ter.
~ ; : 2-~aydro~y-4-met~ox~a~ophe~o~e : 2:g. ~:
; ~ Emul~ogen I~ /Ho~h~t/ ~ :0~50 8~
~ Emul~en~N /~o~Qh~:t/~ 0-50;g- ~ ;
, : E~cm~æ__ 16 : .
: ~E~hyl l,l'-diphenyl-acorylon~t~iIate: ~ ~2 g:. -Pol~o~y~b~len~e-~orbi~ane_triola~t0~ ;l g.
P~lyo~yebhyl~e or~itQ~-mono~earate ~ ~0,5:~
le~e ;~
Q~0 ml.
~; ~Ethylh~x~ iphenyl~ ylonitrilate 2 g~
Polyo~yethylene-~orbi~ban0-monool~ate~;1 g.
:~ ~po~yo~y~hyle~e-sor~itBnff~tri~tear~te .~l g~
yl~n : :- ' ' . : . . 10.0 hglhe~yl 1~ d-~phe~yl-aor~lonitrilate ~ 8 Polyoxyethylena sorbitane-monoole~te - 1 ~.
~e /Y~
.
, , - 27 ~ ~ .
.
~orbitane~oleate 0O5 g.
Xylene _ 7.1 ml.
10~0 ml, Meth~ cyano- ~-methgl-4~m~tho~y~i~nam~t~ 2 g~
Me~hanol 1.5 ml.
~Polyoxy~thylen~-~orbitan~olea~e 1.0 gO
Sorb~t~ne tr~oleate 1.5 g, ~yl~ne ~_7.2 ml - - lOoO mlO
e 20 5-~3~3-~im~thyl-~ orbornyliaene/-3--pentene-2-one ~ 2 g, Polyo~yethylene-sorbl~ane-Qleate 1 g.
Polycxyethyle~e-sorbitane monostear~te 0~5 ~0 Sorbita~e t~i~tearate 0.3 ~.
I~opropanol . 0.4 ml~
Propylene glycol . 0,4 m~.
,, I .
~ yle~e ~
- ~ , 10 ~, O ~ s~
.:' ', ~ ' .
, .
. 5-/3,3-Dimethyl-2-no~b~rn~l~d~ne/ 3-pen~ene-2-o~e 2 gO
~: Polyox~ethylene-sorbitan~-trioleRte 2 g., ~o~ropanol 10.0 ml~
2~
.
~ 28.
;
: ~ 5 66 % I~opropylmy~i~t~t~ ~o1uti~n ~5-/3,3-dimethyl-2-norboxnylidene~
p~te~e-2-one : 3-5 ~e~
~Po1yo~y~hy1ene~aosbita~e-ole~o ~ 1.60 5~o P~ly~e~hyla~;e-~orb~tane-monol~ura~ 0.-30 ~.
- . ~... . . . ~
S~r~i~ane mono~earat2 0.3 ~.
I~apro3~ 0 ~, 4 ~
Propyle~e glyool ; 0.4 ml.
Xylen~ .2~1.
0.00 ml.
6`6 Yo: Isopropyln~ tat~ ~olution o~ 5~ :
an atmosphere of steady oxygen-carbon dioxide ratio. A disadvantage of this method is that the volatile substances enhancing ripening and other meta-bolites (carbon dioxide, ethylene, etc.) formed during storage must be removed. The installation of such a cooling store equipped with ventilation and other instruments is rather expensive and greatly increases the costs of the fruit. Another, more serious disadvantage of this method is that when removing the fruit -from the store it begins to spot rapidly, and becomes very spotty when it reaches the market (Smoch, P.M. and Blanpied, G.D.: Proc.Am.
Soc. Hort. Sci. 73-77 /1965/).
The invention aims at the elaboration of a novel method and a novel composition which enables one to prevent apple peel spot more effectively and more simply than the hitherto known ones.
According to the invention there is provided a composition for the prophylaxis of apple peel spot which comprises at least one light-protective agent together with a carrier, diluent or other auxiliary agent useful in plant-protecting compositions and at least one other biologically active substance. !
According to a preferred embodiment of the invention there is provided a composition for the prophylaxis of "Jonathan" peel spot, which contains 0.05 to 99.5% by weight of at least one UV-absorber together with a carrier, diluent or other auxiliary agent useful in plant-protecting com-positions and at least one other biologically active substance.
r~
6~;~
'rhe inven~ion i~ b~ed on the recognitlon ~hat when ~ppleæ are treated with Q compo~3itlorl containing at least one llght~proteot~v~ agent" pee~ ~pot c~n b~3 elin~inated comple tely or at lea~ t reduced to the mini mum, - q'he ma:Ln ad~a~ta~e OI the proce~ ~nd composi-- tion accordin~; to the l~ventlon over th~ known O:tle9 -i~ -th0,t evon a ~in~le tre~tmeIlt i~ geIlerall~r ~ufficl-en~ to prevexlt peel ~pot prao ~ically comple~elyO
I t i~ lmport~nt ln th~ large-~cY,le hor ticulture ~ but e~r;on.~or ~mall-p~:rcel owner~ th~t only a ~l.ngle 3pray treatment is required:instead o~ e,g, f:~vo treatmontsO
A ~urther advantage of the method and ¢omposi~ion acoording ~o the invention ia that the apples are p~eserved even a~t~r ~tora~e in ~he wlnter season~ that ls they ha~e a lasting re~ult in con~ra~t to the C~-~tora~e methodO ~oreover, the ~rult pulp doe~ not ~o~t-~en a~ after the~ -ray treatment. Another signi~icant ~dvantag~ i~ that ~h~ novel method of ~he in~entton .
doe~ not rcqulre ~y ~p~cial~in~tallatlon ~n~ equlpment~
~1nee th~ spraying device~ alre~dy ln use ~n be Qp-plied~ It should be mentionod a~ a specific ~d~nta~e - that the oral to~i¢ity o~ ~h~ u~ual li~ht-protect~ve ~erlts is very 1 OW9 i E~ any., .~ , .
~ 6 ~
; The light-proSeotive agents applied ~n the method and composition of the invention are known compounds~ Some o~ them are applied :Ln the plaætic :induætry aæ IJV ~tabili~eræ, whereas other~ in the ~ield of coæmetic~
On the basis o* their fu~cti.on~ the light-protective ~ent~ oan be classifle~ e.g. ~ ~ollows:
light screeners, UV absorberæ, qUenCher9 ?
radic~l sca~engers, and perox-ide d~co~posers~
IIo~veverg i~ is more appropriate to cla~si~y the lit~ht~protective agent~ ~ccording to their chemLc~l - struc-~ures~ since a lit~ht-protective agen-t may have more -than one ~uno-tion.
The l.i~ht-pxo-tective agents; i~e. tlle active agen-ts o* the co~position~ accordin~ to the in~ntion can be selected e~g~ ~rom the following oompound typeæ:
benzophenoneæ, benzotriazoles9 dibenzot,riazoleæ~ tri-tri~Y,olobenzene derivatives~ aromatic estern~ substi-tuted acrylonitriles 7 met~lorg~nic compolmds, alic~clic - dienone derivatives9 furthermore certain inor~anic pi~-ments~ etc~ The compositions accordJn~ to ths inven-tion may ~lso contaln more than one ligh-t-prot.ective agent~ ~nd they may belong to -the ~ame or dif~ere~t chemical groups~, Thus, the inve~tion relates to ~ proce~ for the prophylaxis o~ apple peel ~pot, p~rticularl~ peel ~pot of ~pple~ of "Jon~than" v~rlet~ characterlzed in that the apple i~ treated wit~ E~ compo~ition conta~n-ing ~t least one li~ht-protective ~gent, optiQnally at least one other known blologic~lly activ~ sub~tance ~nd optiona]ly one or more car:rier, diluent and/ or auxiliary Elgent common.ly applied i~l ~uch composition3.
Furthermore, the invention relates to a novel compo~i-tion which contains at least one light-prot~tive agent, optionally along with at ~east one other known biolo~ic~lly acti~ sub~tance and with a carrier ~bind-ing agent and/ or auxiliary agent commonly applied in ~uch compo~ition~.
Accordin~ to the method of the invention the novel composition, preferably in diluted form, is ap-plled on~o the apples pref~rably on the tree, iOe.
baIore harve~t, but one may also treat the ~pple~ alre~dy har~re~ted .
In accordance with the invention e.g. the following benzophenone deri~atlves can be appllad :
2, 4 - dihydro~yberlzophenone, 2-hydro~y-4-metho~ybenæophe~one~
;26~2 ~, 2 ' -dihydro~y-4, 4 ~ ~d~..methoxybs-3næoplleIlons~, 2 9 2 1~ ~ 4 5 4 ~ -te trahydro~ybenzophenone 2~hydro~y-4methoxybenzopheno.ne-5-~u.L:Eonic acid~
~odium 2-hydro~y-4-methox.ybenzophenone-5-sul~onat~, Z~-hydroxy~4~metho.xy-4'-methy Lb~nzophe~one, 2,2;'-dlhydro~y-4-methoxybenzophe~Qne, 2-hydroxy-4-n-heptoxybenæophenolle, 2-hydroxy~4-n-oc-tyloxybenzophenone~
2-hydroxy-~-metho~y-2'-carbo$ybenæophenone, Z-hydro~y-4-dodecylox~benæophenone, 2~27-dihydroxy-4,4.'-dimethoxyben7lophenone-5-sulfonic . ~
acid, and : : :
2-hydroxy-2'-chlorobenzophenone.
Particularly pre~erred members o~ the ben~o~
phenone derivatives a:r e the following one~:
2-hydro~cy-4-n~octylo:~:ybenzophenone~ ~.
2-hydroxy-4-n-heptyloxybenzophs~ns)ne"
2-hydroxy-4-dodecyloxybenzophenone 2,2 ~`~7 4~4'-tetrahydroæybenzophenone, ~nd 2727-dihydroxy-4,4'-dimetho~ybenæophenone-5-sulfonic aoid~ ~
~: : , In accordance with the :invention e.~. the ~ollowillg bs-3nzot~rlazole and dibenzotriazole delivative~
, .. . . . . . . .
6~2 `.
p~l~ed:
Z-/2'~hydroxy-5'-Methylphellyl-~-berL7otri~zole, 2-/2'-~lydro~xy-5'_n-oDtylph~nyl~-~e~Lzotriazole9 2-/2'-h~droxy-3'-tert.buty~-59-metllylp~onyl/-5-chlorob~nzotriazole;
~2-/2'-hydro~y-3 9 5~-di-~ert~butylphenyl/-5-cllloro-~ ~bonzotr~azole, ~nd : ~
: 5~111I-5~,1l'-dldehydxobe~zotri~zolo L?'9l-af~bénzo-; triazole~ .
Particularly pxe~erred member~ o~ the benzo-tri~zole ~erlva~ive~ are the ~ollowing compounds:~
2-/2'-hydroxy-5'-n-octylphe~yl-/benzotriuzole9 ~2-/2'-h~droxy-3'-te~t.butyl-5'-m~hylphenyl/-5-ohl:or.o~eD~o-triazole~
Z~ 2'~hydrox~-3',5~'-di-tert.butylphenyli-5-ohloro-~
~benzotriazole, and 5,11I~-5',11'~did0hydro-benzotri~zolo`L29 ,l-a ~benzo-tria~ole~
`In accordanoe with:the i~vention e.g. the llowi~&^ tri-triazolobenæene~deriv~tives can b~ :
- ~applied~
;~2,~,8-tri/ph:enyl/-tri-~-triazolo/a~c,e~ b~1lzene, . :
:: :
, ;
- . . ., ~
~ 1~) 2,5,8-tri/n1trophengl~tri-~triazolo ~a~c~ enzene 2~5,~-trifdinltrophe~yl/-trl-~-triazolo /a,o 9 ~/benzene In accorda~ce with ~he ^ln~ention e.g~ ~h~
followl~ aromatic estarn c~n be app~ied~
digalloyl tr~ol~at~
ph~nyl salioylate 9 ~ `
p-octylphenyl ~alicylate9 t~rt~bu-tylphe~yl ~alloyl~te, resorclne monobenzoate, and 2,~4-di-t~ert.bub~lph~n~l 3,5-~dl-t~rt.b`u~yl 4-hydroxy-be~n~oa~e.
Pre~erred repr~entatiro~ of th~ aromati¢
~ te~ de~i~ati~ea are th~ followi~g~ompound~:
dig~ o~l t~ioleate, p-oct~lphenyl ~alicylate, re~or~inol monobenzoate, and ~ 2,4-di-tert.butylphe~yl 355-di-tert butJl-4-h~dro~y-~i~ ~ be~nzo~te~o In ~c~ordance with ~the invention e~gO th~
~ollo~i~g ~u~titut~d a~rylo~itrile der~vativ0~ ¢~n be ~applied:
eth~l~ diphenyl~acrylonitrilat~
2-ethyl-~e~l 1,19 d~henyl-acrylo~i~rilateJ
meth~ oyano-~ -m~thyl-4-methoxycinnamabe.
.
z Pre~rr~d r~pre~erltatives ~f th~ ~ubsti~uted acrylonitrile deriv~tlve~ are the ~ollowIng compounds~
eth~ diphenyl-acrylQnltrilRte~
2-ethylhexyl l,l~ diphe~yl-acrylonit:rilate~ and methyl~ -cy~no-~ -m~thyl-4~metho~ycinrlamata~
In accordsnce wlth the ~nve~icn e.g~ tha ~ollowing metalQr~anic compound~ c~n bo ~pplied: :
~2 9 2'-thiobi~/4-tert~octy].pheno.Late~ - n-butylamine nickel /II/, ~
B nlckel bi~octylphenyl ~ulf~d.e /~erro ~ lOl and A~ 106 ~ 9 nickel dibutyldlthiocarbamateg f3,5-dl-tert,-butyl~4~hydroxyben2yl~pho~phorio acid mono0thyl~ster 2:l nickel chela~ei Irga~tab ~002, cobalt /II/ di~yolohexyl-dithiopho~phinateO
Pr~ferred member~ o~ the met~lorganic com-pounds are ~ ~ol~LQws:
/2,2~-thiobi~/4-terb~octylphenolQ-te/ -n-butylQmine-ni~:el /II/, and nickel~hi~oc^tylphenyl ~ul*i.de /~erro AM lOl and : Ferro ~-105 /.:
Of the alic~clIc dienone derlvative~ 5~/3~3 dimsthyl~norbQrnylidene/-3-pentene-~-o~e c~n be ~p~
pli~d to ~reat advantago.
/ r~ lc In accordance with ~he in~rentlon ~g~ tha follow:~.n~ inorg~lic pigm~nt~ can ~0 appliads c~bc~n black, tit~n~um dio2ide, and ~in~ o~ ide O
Particularly pre:l~erre& member~ of ~ho i~organic pi.~;m~nt.~ are e.~;~ t-ltanlum divxide and zinc ox:lde.
The me th.od of ~he inv~ntlon al~o permit~ tho u~e o:~ compo~i t:i on~ wh~oh cont~in~ more than one ll~ht-..
protective a~nt99 ~uoh a~ one or more b~nzopheno~eand/or one or more benz~tr~a~ol~ ~ndfor on~o~r mvre ~:lbenzotriazole~andtor one~ or moro t~iæ-tria&oloberl~e~e : deriv~Lti~re~ axLdtox~ one or mor~ aromat-l¢ e~erJ~i and/Qr -~o ~e or more ~ubstituted acrylonitrile ~nd/or one or more metalor~anic compou~d/~/ ~nd/or orl~ or mor~ aliph~
- . , Rtio dienorle derivative/~/ a~d/or one~or more l~orga~i¢
: pigment/s/.
:~ :
Thes~ composi-tions ~cGordi~:Lg to th~ inv~ntion - -oontaining more than orle: ligh~-proteotlv~e agent~ m~y contain e~g. th~ ~ollowin~; ~ombi~aation~ o~ active :
~gents:
2-/2 ? -hydroxy-3 ~ -tert .,butyl-5 '-me~hylphenyl~-5-,chloroben~o triazo le and 2-/2'-hydro~y-33,5' di-tert.
bu~ylphenyl/ ~5-ahlorobenzotrlazole, zinc oxide and 2-/23-hydroxy-39-te~t.but~;5'~methy1 phenyl/-5-chlorobenæotriazole, -~ L~ -292'g~41--t~tr~hyd~oxy~erlæo~herlono and 2-hydro~y~4-methoxyb~nzophenvrle~5~sulfonic aci.cl, 2~ethyl-he~rl 1,l7- diphonyl~acrylonitril~te ~nd 2 h~droxy~4~m~thox~benzophenone~
5-33 9 3-d~me-th,yl-2-norborn~l~d~ne/-3~pentene-2 one ~nd Z-hydro~y~4-n~oc-tyloxybe~nzoph~none 9 2-hydroxy-4~n-o~,tylo~y~enzopll~none and 2 /3'-tert.
butyl~27-hydro~y~57-methylphen~l3~5-chlorobenzo~
~riaæole, 5~/3~3-dime-thyl-2-norbornylidenej-3-pentene-2-one d ælnc o~.ide~
-/313-dimethyl~2-nor~ornylidene/~3-pentene-2-ono and ~.ig~lloyl triole~-te~
2-ethyl-~e~yl l,17-dip.henyl--acrylonitrilate and 2-hy~roxy~ n~oc t~loJ~ybenzophenone ~
2-hydro1ly~4~ oG-tyloxy~ 3n ~;ophenone 9 2~f3~ ~ert O
buty1-29-hydro~y-5'-me~hylphe~yl~-5~chlorobenzo~ri-a~ole ancl 5-~3 7 3-dimethyl-~norbornylidene/-3-pen~en~-_~-one, 5-J3 9 3 dimethyl~2-~lo~bornylid@ne/-3--pentene-2~one ~nd nicke~ blsoct~lphen~l s~lfide /~erro AM-101 ~Z-/2:'-hydroxy-3~5'-d~--tert~bu-tylphenylf~5-chloro-~enzo~riazole ~nd ni~kel b~soctyl phenylsul.~ide ~e~ro AM 105~ 9 2;r~2)-hydro~-37~5~,~di-~er~Obutylp7lenyl/-5-chloro-~ 2~Z
- 14 ~
ben~otrlazole a~d~/2~2~- ~hiobi~ n-octylphenolat~/
-n-bu~lamine n~okel /II/ 9 2-e~hyl~hexyl l~l' diphen~l-aox~lonitrllate and ~2925-thiobi~4-tert~octylphcnol~e/-~-but.yla~ine-nickel j~ abc~
should be ~tre~sed9 howe~er, that:the abo~
li~t~ ~f li~ht-proteoti~re agen~æ and combination~
are not e~haus~i~e~ ~ince other light protec~i~e agent~ ~nd combinatlon.~ ca~ ~lso be ~pp~ied~in~the method ~nd composition a¢cording to the inve~tio~
Th0 above li~t~:~e~e merffly ~o lllu~trate ~he~in-v~nt~on.
:
: : The light-proteotive ag~nt~ themselves~o~
; ~th~ir mlxtu~es are Gonverted ~i~to compositlon~ ~nd the`:re~ult~ ¢omposition~are ~pplied ~ a~ent~
~or the preventlo~l o~ apple pRel~spot.
. The ligh~-protective agents themsel~e~ or their mlxtures c~n be converted into conventional -~oompo~ ion~ such a~ wet~able spray powder~ /WP/~
lowable ooncentrateæ /particularl~v water-~oluble .
p~wder ¢onc~entrabes, wate~-soluble~sol~tion concentr~
:~ ~ te~ ~WSC/~ emulsi~ya~le~ concentra~es /E~/ or compos:i-: tion~suitable for ultra-low-volume /ULV~ ~pp~ica-tio~, $he cQmposit~ons ~re prepared accord~n~ to woll-kn~wn methods, e.g. b~ ~dmixin~ the light-pr~-, .
, tentiv0 ~ or ~i:~tull~e~ th~r~oll:' with l~erl;~ 2~01~ld os~ r~ D ~ U0~ I' oth~r a~ 0 ~o b~ ~ 0~ ~k~ 3~ t~i~S~ p~
~d d,~p~B~g ~ o ~ $r~ 9 ~nt~c~
~dh~3~ n~ g~ p~ a~ or ~a~tai~ial~ o:~ improvl~g the b~ logllo~l a~ti~r:Lty9 Q~ti~-3Lm~ s p A ~ol~d ~ri~lDr3 or d:Llu~Ilt~ ~" g~ th~ ~ollow--i~ subs~t~ oa~ b~ appl~d s ~e~r~ ts~ral and ~s~the~l~
~illoats3~ p 3:i.1il.0~ s a;:ld~ ox~ ~odi~lecl clay m~ ral~ and b E3nto:~i t~ c~ ar~o~t phO8phat;1El~;p 0ti8~" e~gO dlatom;~Lo~ou~ carlth~ d~lo~ teg oal~c~
~ag~ m o~fl~ ç
: ~ O:f ~he lls~ d oarrie~ dilu~ d ~l~e~lts 0O~0 w~4ter" C~rga~io 901~eI1~3 a~ld tll~ tUrel~i ~hereo~ Ot7L
a~3 alos>hol~3 ~ e.~ tha~93. ~:~d e~ha~l eto~ ) ~, glyoo3.s .
(21UOh a~ ~ly~erinE3 ~tc~ t~n-3~3 Cs3aLch a~ d~me~hyl keto~e~
m~t~yl~ethyl~ to~ o,, ) ~ e~tor~ ~ ~uoh ~s e~llyl acetateg ~_ ~d ~obutytao~tat~, amyl aoe~a~a eto,, )~ laotone3 ~suoh a3 ~butyrolacto~e et~ ) 9 la~t~ms ( r3uch a~ amino capr~ -~) la~ 3 ~o~ d~ g ~u~h a~ ma~h~r7 ~rm~ d ~ . 3 al~p~ÆLtlo; oaclic a3~d aroma~c ~r~6~ax~bo33~, arom~tlo-~al~phat~ h~rclrocar~o~s ~auch ;E~3 h~3ptane, he~a~e9 cyolo~
he~ e, :~ylen~, tolue e e~c, ~ ~d th~ ~;c)lv~tl!3 de~i~ated wi~ shell~ol9 No~a~ol et~, oan b0 m~ntio~led.
The w~3t~:~g~ ~ls~ 1~,e and ~m~ Ey:lO~g ae~$~39 i')1arl~
~` 16 ~
~dhe~3i~e~ c?~lc:L~ a~d a~t;~ t:lLok~ enlta oatl l~e o~ lonio alld ~oll_il o~in o~arQOtar~ The ~ub~ta~oea o~
~o~1o ohar~ter o~ lbe aalio~ s, oatioll:Lo a~ amphot0I~.
~he ~o~io ~ t~oç~ h~ ~Ql~ ar~ ~o 11 ~s~tio~led s 3ul~a~e~ ~d ~:he1r ~alts S, sul~o~at~ a~
~heir ~alt~ oh as laur~l ~ulfa~e~ a~d lt~ ~alt~, be~:~e3ul~0~ate~3 a~d their ~alt~ petroleu~sulfo~ate~
a~nd their salts, soap~ e.~0 :3odilam ~o~r~t~, e~oO
0~ ths~ ~o~_io3~io ~ubJ~anoe~ e,g" the ~ollowi~g ar~ to be me~t~ o~ed ~ blook polyaler~ t~f etb~y~e~Leo:~ide a~d E~opyl0n00æ~d ~d t~eir ~ter~ or e~hers a~d the a:latural or lly~'chutlo oli~oro~oleou:Lnr ~ub~lb~roe~;.
~ .17 ~
Wettable ~pr~r powdsr~ can be pr~pared e.~ .
by ~srindi~ the ~olid light-proteotive agent/~/ ~nd the o~her au3 :iliary ag~xlt/~ ? ~ur~actaIlt/~J a~ld:
, a~ t~/ fo~ main~ainin~; or ino~e~in~ th~ blolo~ical ~aot~ by ~o a particle ~ize o~ preI~r~bly below~100/um~, p~rt~ular:L~ bolo~r 25/um.~ and homogeni~in~; ths ~ro~nd ~hstQn¢e~- ~ Wlth llquid ~f~ct~t~, on~ oan 8190.
proceed by applyin~ the liquid surfaotan~ /e.g. by a~omiæing j onto th~ ~olid or~;anic or min~ra~. diluo~t~
or onto ~he powder~ m~:ctur~, p~o~erably below lOO,!,um., :
.
part:iGularly below 25~ n pa~ticle ~iæe~ al~eady~
: c~ntaining~th~ æolid light-prote~tlve agent/s/.~ :
A a~i~ilar prooedure o~ be appli~d ~ith liquid li~h~
pro~eo~tl~e age~t/~ ettQbl~ ~pray:powder~oan al~o -`
be prepared by homogeniz~g:~-the ~round component~
oompr~in~ th~ homo~eneous ml~ture e~OE. on a roll~r ~mill, and then grinding -the compres0ed substance ~o th~ par~ioIe ~lze give~ abo~e.
Water-~oluble powde~y conc~ntrate~ can ~e pr~p:ar~d e.~0 bD grindin~the solid water-soluble proteG~ive agent~ , solid sur~aotant~/ and other zolid add~t~ve/sJ ~eparate~, and homogenlz~n~
h~ ground sub~ta~oe~ When liquid surf~ctant~ are : ~
~pplie~9 one ~an also proceed by ~u~pendin~ t~he pre ~iou~ly ground solid compDnents ~n ~n organi~ ~ol~ent 6~;~
.
oont~ining o~e~ or more li~id ~uriea~ba~t~u/ 7 ol~d l~hen :dr~in~; th~ ~u~p~ o~ e.~5. bJ ~prayin~ ~, In this w~r ur~ta~ pl~ea orlto th~ ~3U:rI QCe of ~e~
ol~id~llght-prot~ re~a~ ~d~the ~ d d~lu~nt.
ul~i~yable~ ~o~rloèntra~e~ a/ ~appl~c~
~f~r ~he prQ~ràtlcin ~o~ di~pers~bl~ OU~3~Bp~l àmul~ions ~an~ be pr~pa2~d by ~di~s~l~ring :~on or ~ re it~ro~o~v~ sg~n1i~ and ~s ~r~ em~
ing~a~ér~t Qa ~finéd~abo~e in a wa~ olble ~olverlt. The re~ultin~ emulsi~yable~ ~uon~tra~t~
emul~lon:with wa~er ~i~hor sp~ ou~y or upon; a llght m~ohan~oal i~bex~entl~ ~d th~ ~r~ul$~
liq~d~ ~uls~0n~0~n be ~1~orea :~r: i~::prolo~d~
per~~o:
Water-~olubl~ ~liquia~Go~eI~r~ $~ ca~
be ~a~;red ~y d~s~ol~ ; t he l~ prot:eoti~age~
d ~tha appropriate-w~ter-~olubl~ a:~r a~en~
in w~e~: a.nd/~r in ~ wa~;er-ml~cible ~olve~t. :~A sp:~y .o~u~tion o~ the desi~ed ~onoent:~lon c~ b~ pr3par~d by~ d~lution ~ith~water~
ith~appropri~te ~amul~ifyi7~ a~en~ on-rtr~ted-~qu~ou~ ~olutlon o:~ ~h~e ~l~t-Prot~stiYa .t ~ o-:be~ përaed in:~a wa~ o~le~;
lquid~ t~ p~epare l~er~a emul~ion~ hu~ he oper ~sol~tlon~ of th~ ~so~ven~s ~d ~ aet~C~, ..
- . ~
- 19 ~ 6~Z
light-protectlve compo~ition~ ~ppl~ca~le in bhe ~
~ulture for ~he prophylaxi~ o$ ~plpl~ p~el ~pob c~n ~be pr~pared5 wh~ ch compo~itio:n~g whe~ admixed with -wat~r or a~w.at~r-lmmi~e~lble llquid~ ~o~m dl~per3~ :
ey~tem~ /ev~n mol~culBr dlsper~on~ able ~or~pro-longed:perlod~
: ~ Spray ~olution~ oan be prepar~d:in -B kno ma~n~r b~ dil~ g ~he light-prot~at:i~e~cQmpo~itio~a:~
:
w-~th ;tYatar~ ~he ~pray ~olution~ contain the li~ht-:
-p~o~ective agéntfst ~o~erally in an ~mou~t~lower th~n 5 % b~ weight~ p~r~icularl~ ln~n Qmount of l:to~
0.1 a~o by wel~h-b. One o~n;al~o:proc~ffd;by:.~irst pre--parlng ~pray~liquid~ which ~on:~ain only a~:3in~1e light-proteotiva~aee~t, and th~n poolin~ ~he~e 11-qu.ld~ ~e~ore u~e O
he compositi~-n~3 aoco~rding to the invèntion~
w~r~ :screen~ by :u~in~ ~p~aD li~ids a~ describè~
abc~e~; E~ch o:e the compositions were ~est~d g~ne~
ally on l~O ~pple~ ~a~ follows~ ~ thg applé~ ~werè im-mer~ed into about ~ 1~ o f a~ ~pray liqllid, r~mo~ed ~a~t~r ~b~ut 1~ mlnu-te, allowed ~Q dr~, and then irr~dl-sted ~ur:Eth~ a ~Tu~gsram 11 Ge~nlcid ~F" type ~ meroury l~mp /wàv~leng:th r~g~O 1~5 -to 578: ~ Erom ~ d~tance OI
~4~0~: cm~Dependi~g on their colour~nt ¢ontent~, t!he `~
appl~~ were i~radiated for 1 to 5 houre; the ~o~e-b ~r r~le ~la~K
~0 ~ ~ 6 cololl:red a~)pl(?~ w~x~e ,~ner& 11y i.rrad lated fo:r f~hort-l Q:r ti.rnes ~ rrh~ lrracli~ l;ed Flp~le~ alld the non ~irra(~iat-ed ones 3er~illg ~S coni;rol~ were .s tored for 2 morlth3 at 4(~ and tl!len the rc~u Lt~q were ~v~lunted. q`he spo t1 on t~Ic i rrad~ ed ~ides of the applc~ a~pcar ~mul-tarl~ou~;ly with the na-tural peel spo-lis~ consecluerltly ~h~ ~o~re ~cre~n:ing method i~ in~-~irm co:rr~lation with Lhe :Eie:Ld oxp~ri.ments.
:~n -the -Pie:l.d e~pex irnoIl-t~ the ~pple tree~
wer~ sprayed sorne weelcs /pre:~erably 3-to 6 weekG/ :be~ ~ -l~o:r e harvQ.s li . Depend.irlg on !ih~ stren~; th of sun~hine the trees w~?re ~prayed onc,e or tWiC~?- GeIl~raIly e~en ::
one ~pl!~ayin~ p:ro~ides ~go(~d r~sults. When there is .
st~oll~r sunshin~ dur:intg r:Lper~ g, i t: is pre~erred to use ~a ~pray liquid wi-th iIloreas~d UV absorber con-~cen-trat:ion .in orc~er -~.o eliminat,e thc~ need OI double sprayin~r~
1~ well~proved teclmique o-~ spray in~; accor~ing to th~ in~ tion is the soaking me~thod.l This m~thod requires 2 ~o 10 li-tres, preferabl~r 3 to 7 litres ~OI
~pray liquid per~be~rer un~i.t~ ~he tern~ ~Ibearer unit"
refer~ to the ylelding area /re~ard~Less v:E t;he sub~
jec-t ~ varie ty ~nd ar~e / which can b~ sprayed in a~ ;
~ingle spraying~ with 15 lo o-.E l~quid, takin~; into account th~ spray~n~; efPic:iency OI ~ ba t~ery spraying ~;P2~i~2 - 2i ~nachino with 1~ 5 mrn~ n~zzle bores a~ 8 atml, ln~tlal-pressur~ /Agr-lcultural I-exicon/ MQZ~ga~daSa~;~ Le~
kon~ NlezQgazdasagi Klado, Budapest, 1958; Vol. II, P~ 593./ 7 The in~Tention i~ elucidated irl dat~il by: the aid o~ the f ollowing non;~l~mil;iIlg Ex~le~"
x a m p ^1 e ~ .
2 9 ~-DihydroxybenzQphenone /par~icle s~ze ~low lG/u~
Highly di~per~e ~lc1¢ acid /Ultra~
Aero~il, DurosilJ ~3 %
EQoli~ 42` %
~HOE 8 1880 /Ho~ohst; ~odiu~ salt o~ an sliphatic sul-f onic ~¢ld~
HOE S 1998 /Eo~c~t; f~tty alcohol~poly~
4.% ~.;
glycoleth~r e lQ~
2~2~-Dihydrox~-4j4~-dim0thoxybenzophenone /paYticle size: b~low 10/um/0 ~ 20 %
Highl~ disper~ ~ilicic acid ~Ultra~
~eros1lq Durosil/ ~ 35 %
Kaoline ~35 %
Tri~on ~-100 /~ohm a~d lIaas; octylph~nol~
~r~ C
Z~32 , poly~l~col.ethcr~ 5 ~o Sodium lauryl~ulate 4 %
Pol~vi ~ lpyrrolidone K gO /GAF Corp~
~00 %
Exa~ple ~
5,11H-5'~ ideh~roben~o~ria~olo-~9 71- ~benzotriaæole /pàrt~cle.~ize~ below 20/um-J . ~ ~ %i Kaoline ~o~ %
Silioa gel o~ great ~urface area ~5 %
~onylphenol-polyglyool~her /E0 ~15 / 4 %~
Polyvi~ylpyrr~lidone K-90 /GAF ~orp./
:' 100 ,~
2~/2 ? -Hydro~y-3'-tert~but~1-5~-meth~lph~nyl~--5-ohlorobenzotrlazo~ /particle ~ize: be~
low 20~.um~t ~ 45 %
2-/2~Hydroxy-3',5'-di-~er-t~butylphenylJ~
-chlorobenzotriaole~/p~rt~cl:e siz~e: below ~ :
}O~um.~/ ` 40:% ;`
: Siliea gel o~ ~xe~t ~ur~ce ar~a ~ lO ~o Nonylphenol-polyglyooleth~r /E0 15~ 4 %
Poly~inylpyrrolidone K~90 ~GA~ Corp.t 1 ~
100 %
:~ , m~
Zlnc o~lde Jpa~ticle ~ eO ~ 5~um~/ 90 %
Ga~a~ ~M-710 /G~F Corp./ 2 %
Tri~thanolamin~ l %
Silica ~rel o~f ~roat ~u~face arQa /Aero~
~uroqil~ Sup~rsil, etc/ 5 %
Poly~inylpyrrolldone ~-90 /G~F Sorp~/ ~
100 %
~no o~icle /par-t~cle size~ below 5~um./ 60 ~o 2-/2~-~Iydroxy 3~-tert.butyl-5t-me~hyl~
phen~ 5-chlorobensotrlazole~ ~ . 25~%
Sil~o~ gel o-~ g~at ~ur~oe area ~Aero~
Durosi]., Supersi~/ ~ 5- %
001-.~lph~nol-poly~lyc~le:the~ ~0 lO~ :6~%
E-kha~olamlne ~al~ o~ Ga:fac RM-lO /~' Corpc/ 3 %
Roly~inylpyrrolidonQv K~90 JG~' Corp./ ~ ~
100~ % .
~ . .
2~Hydro~y-4 mcthoxyben~ophenono-5 ~ul~oni~
.
acld ~ ~ ~ 7-5 %
Sodiwm c~rbo~ata 81~ 20 ~%~
Sod~um d~oc tylul:Eo~u~c~at~ ~2 ,$~%
Pol~vlnylpyrrolidone K~90 fGAF Corp~
lOOoO %
~sl~ rl~ !
.
z ~ 4 2 1l 2 '~DihydroE~-4, 4 ~-dimetho~:yben~ophenone-~5-~U1fOniC aCid ~Od1~ a1t 90 %:
SOd~ diO~tY1~U~ UO~in~t~ 5 ,S
PC 1~1nY1PY~rrO1idOne K-90 -J~F Corp~
~0~ ~ .
2~, 2 ~ ihydroxy~~ dim~tho~ybenæophexlo~e- : :
-5~-~ul~Qnlo ac~d ~odium ~a] ~ 90 Sodium ~i meth~l~ol~ taurimide 5 ~HyarQxy~th~rl cellulo~e~
, ~
2~Hydrox~-4-methoxybenzophe~one-5-~ul~
~onic ~-cld~ ` 75 ~%
: Sodi.um carbo~at~ . ` 20 %
Sodlum d~oc ~ylæul:Eo~llc¢lnate 100 %~
Hydrox~4-metho~ybenzoph~none-5-~ul-:
- :E'o~i~ ~old ~ 2 ~;0 -Tri~ thanolamine ~ ~ g.- .
. Ga~ç R~a-510 /GA~ Co:rp./ ,5 ~
Ethanol 5~9 ml~.
W~l;ex: _l ml.
10 mld, - 2~ --~,~ "
2,~'j4f4~T~trah~dro.~nz~phen~ne 005 ~.
Z~~Iy~ 4-m~th~ ~n~h~none-5-~ul~oni.~
cid . ~ 5 g.
l'r.iebh~lam~e 0,75 ~faIac ~~ p ~,Yo~p~/
Methano~ ~ ml~
Wa~er l,ml~_ ~ lO.O~mlO
2 ? 2~4j~-Tet~ah~oxyb~zopheno~e~ Z ~.
h~olam~n~
~P~l~o~yethy~ or~i~ane-mo~op~lmit~e~ ~ ~ 2 g.
~t~hanol 10.0 ml~
2-Hydroxy-4 m~thox~benæoph~non~-5~ul*onlc :
: a~
O
9~'~ 4~-Te~rahyd~o~benzQphenone l:g~:
~ rie~anolamin~ ~ 0~5 g~
`~ rolyoxy~thyl~n~-sorb~ban~-monopalm~.t~te 0~5 g.
'510 /GAF Gr3?~ -5 B~
hanolami~e monoQl~a~e O 0 5 ,g., -opropanol 1 ml .
, , .
~ 6 _ 2 Me~hanol .
: N.0 m~.
~h~ oompo~ition ~o~m~ ~ oollo~dal ~olu~io~ ~it~ w~ter.
~ ; : 2-~aydro~y-4-met~ox~a~ophe~o~e : 2:g. ~:
; ~ Emul~ogen I~ /Ho~h~t/ ~ :0~50 8~
~ Emul~en~N /~o~Qh~:t/~ 0-50;g- ~ ;
, : E~cm~æ__ 16 : .
: ~E~hyl l,l'-diphenyl-acorylon~t~iIate: ~ ~2 g:. -Pol~o~y~b~len~e-~orbi~ane_triola~t0~ ;l g.
P~lyo~yebhyl~e or~itQ~-mono~earate ~ ~0,5:~
le~e ;~
Q~0 ml.
~; ~Ethylh~x~ iphenyl~ ylonitrilate 2 g~
Polyo~yethylene-~orbi~ban0-monool~ate~;1 g.
:~ ~po~yo~y~hyle~e-sor~itBnff~tri~tear~te .~l g~
yl~n : :- ' ' . : . . 10.0 hglhe~yl 1~ d-~phe~yl-aor~lonitrilate ~ 8 Polyoxyethylena sorbitane-monoole~te - 1 ~.
~e /Y~
.
, , - 27 ~ ~ .
.
~orbitane~oleate 0O5 g.
Xylene _ 7.1 ml.
10~0 ml, Meth~ cyano- ~-methgl-4~m~tho~y~i~nam~t~ 2 g~
Me~hanol 1.5 ml.
~Polyoxy~thylen~-~orbitan~olea~e 1.0 gO
Sorb~t~ne tr~oleate 1.5 g, ~yl~ne ~_7.2 ml - - lOoO mlO
e 20 5-~3~3-~im~thyl-~ orbornyliaene/-3--pentene-2-one ~ 2 g, Polyo~yethylene-sorbl~ane-Qleate 1 g.
Polycxyethyle~e-sorbitane monostear~te 0~5 ~0 Sorbita~e t~i~tearate 0.3 ~.
I~opropanol . 0.4 ml~
Propylene glycol . 0,4 m~.
,, I .
~ yle~e ~
- ~ , 10 ~, O ~ s~
.:' ', ~ ' .
, .
. 5-/3,3-Dimethyl-2-no~b~rn~l~d~ne/ 3-pen~ene-2-o~e 2 gO
~: Polyox~ethylene-sorbitan~-trioleRte 2 g., ~o~ropanol 10.0 ml~
2~
.
~ 28.
;
: ~ 5 66 % I~opropylmy~i~t~t~ ~o1uti~n ~5-/3,3-dimethyl-2-norboxnylidene~
p~te~e-2-one : 3-5 ~e~
~Po1yo~y~hy1ene~aosbita~e-ole~o ~ 1.60 5~o P~ly~e~hyla~;e-~orb~tane-monol~ura~ 0.-30 ~.
- . ~... . . . ~
S~r~i~ane mono~earat2 0.3 ~.
I~apro3~ 0 ~, 4 ~
Propyle~e glyool ; 0.4 ml.
Xylen~ .2~1.
0.00 ml.
6`6 Yo: Isopropyln~ tat~ ~olution o~ 5~ :
3,-3-dime~hy1-2-no~bo~ 1de~ 3~
pe~t~ne-2-on~ : 3.05 g.
Polyoxy~t~y1sne-~orb~tane-o1~te 1.0 Polyo~hyl~na-~sorb1~ane-8t~arat~ 0,.5 ~-Sorb~a~e stear~e ; ~ 0 . 5 g o ~yle~e~
~,, . ~ ~. . . -/2 j 2 "-T~obis-J4 i;~*t, o~tylpl~enc~late//-butyla~n1n~-nlck~l~ JI~ - 2 ~;0 l!~o}~T~pli~ol pol~gl~o~hor /;~Q 10/ - 108 g~
.
10.O ml.
_ 29 ~ ' ]:~ enple 2~
Nic.ke~bi~octylphenyl ~ulfid:e /FerrQ
~M 3.01; Per~o Chomical / 2 e~
~ Nollylphenol p~ly~lycoleth~r ~0 10/ 1~8 ~.
: ~ ~yl~n~
lO~O ml.
Nickel-bi~ootylphenyl ~ulfide /~er~o A~1~105; ~e~ro Gh~mical/ 2 g.
Nonylphenol poly~lyoole~her /~0 10/ : 1~8 ~.
Xylane .
10.0 ml~: :
; . : ~ ~
e~orcinol monoben30a~e ~ 2 g~:
No~ylphenol polyglycole~her ~E0~0 i l.O g~
:~:Sorb:itane trioleab~ ~ 0.5~g.
~Polyoxye~hyle~e-~o~rbit~ne-oleate ~ ~ 0.5 g.
Ethyl acetat~ ~5 ml.
Xyl:ene ~ : 2.5 m,l.
~ lO.O ml~
",, ~ xam~
- Di~alloyl trioleate- ~ ~ 2 g~
.. . .
~onylphenol polygl~Goleth~r jEO~10J . . 1.5 g.
i ~Sorbitane triolea~e ~ : 0.5 e-:X~l~n~
10.0 ml~
.
. . ~ . .", . - , ~ .
2~2 o~y-~-n-octylo5~yb~1nzQl?he~lone ga No~yIphenol polyglycolether /E0 10~ 1.5 g.
NonyrlphenoI poly~lycol~ther ~0 4-6/ ` 0.5 g~
~yle~ L;~
lV.0 m~0 _~e~ 0 2~Ethylhexyl I,I'-diphenyl~Qcrylonitrilato I.'5 g~
2-Hydro~y~-me~ho~JbeIlzophenone : 0~5 g Non~].phenol polyglycolether /E0 10~ 1.5 g~
~ylene 7.~ml.
. .
~ : 10~0 ml.
66 ~o I~oprop~rlmgri~tate solution o~ 5~
: ~-f~3-dimeth~1-2-norbornyliden~/-3-pe~t-~ ~ ene-2-one ~ 1.5 g.
.
Nickel-bisootylphenyl ~uIfide t~erro 0~ e~ro ~hemO~ g.
Nonylphenol polyglycolether ~0 lOJ 1 gg' atty alcohol polyelycoIether ~ 0~ g.
Polyoxyeth~lene~orbi~ane-~r~oleate 0,5 g.
Xylene :10~ ml~
- ~ 2-~thylhe~yl 1?1~ -diphenyl-acrylonitril~t~ 1 gO
.
~ 3.~ 6~
2~ droxy~4~m~ho:~rbenzophenone 1 ~, Nonylphenol po~yglyooleth~ /EO lOf 0.5 ~a~-ty ~lc~hol po:Ly~lycolether 0.5 g~
Polyoxyethylen~-cJ~orb:itanç3-trloleate 1 g,.
Xylerle 10~0 ml.
~e~
2~Ethylhexyl 1, 1 7 -dlphenyl~acrylon~trilab~ 1 g.
.
2-Hydro~y~4-n-oct,ylo}:ybenzQphenone 1 ~;.
Nonylpheno:l poly~lyoolether /EO 10/ 0,5 atty alcohol po:Ly~lycole~her ^ 0.5 g~
Polyoxyebhylene~sorbi.tan~-~rio-eate 1 e:~
Xylene 10~0 ml~-~pl~
Nick01~bi~0c-tylphen~l sul~lde /Ferro AM-101; Ferro ChemO/ 1~6 g~
2-/2~'Hydroxy-3~5'-di-tert.butylphenyl/-~5~chlorobenzo~rlazole 0~4 g.
~onylphenol polygl~cole~her JEo loJ ~5 e.
att~ alcohol polyglycole-ther 0,5 g~ -Polyoxyethylen2-~orbitan~-trioleate 1 g.
~ylen~
lOoO ml.
~ ~2fi9 - ~3~
~ie~el~bi~octylphenyl sul~d~ /~erro ~M-105~ ~rrp ChemO/ 1~6 g.
2-~29-Hy~ro~y~3 9 ~ 5'-di tert~butylphen~
-5-chlorob~zotri~o1~ 0.4 g~
~onylphenol poly~l-g¢olether ~0 10~ 0~5 g~
~tty alcohol poly~lyco~ther 0.5 ~.
:! .
Polyox~thylene~sorbitan~-t~iQle~te 1 g.
~;yle:n~ ~
10 mlO
i /2 9 2'~Thiobi~-/4-t~-t.ootylphe~olate~ n~
bubylamino-niokel~ 6 g, 2-~2~-Hydro~y-3 t ~ 5 ~ -di~tert~but~lphenyl~
-5-chlorob~nzotr-l:azole . ~ 0.4 g.
No~ylphenol polyglycoleth~r 0.5 g~
~at:ty alcohol poly~lycolether 0.5 P~lyo~yethylene-~orbitan~-trioloate 1 g~:
gy1en~
' 10 ml9 2-Ethylhexyl I 7 19 -d~phen~l-acrylonitril~te 1 g.
2~/2~-Th~vbi~-/4-tert00ctylphenol~te//- .
-~ butylamine-~ickel/II/ ` 1 ~, Nonylphenol polyglycolether ~ 005 g~
, ;;
~ 6 _ 33 T~'att~ aloohol polyglycolether O.S gO
Polyoxy~th~.ene-sorbit~ne~trloleat~
~Ho~ch3t A~ 0 X~yIene 10~0 m~
5~3~3~D~methyl-2-norbo~nylidene/-3--pen~ne-2 one ~ 1~5 g.
2~Mydro~-4-n-oct~loxyb~nzophe~one 1.0 g~
Polyo~yethylene~orbltane-ol~ate 1.,0 g. ,~
Polyo~yeth~len~-~orbitane-3tearate 0.3 g~ ;
Isop~opanol 0.5 ml. :
Propylene glycol - ~ 0~5 ml i ~ylen~ ~ 5 ml. _ lO~.:ml, __ 39 ~Di~allo~l trloleate 4 g.
Polyo~yethyl~ne-sorbitane-monol~ura~e ~ g.
o~ue~ ~ ? ~
~10 g.
~ '.
5-f3~3~Dimethyl-2-norbornylide~e/~3-~penten~2-on~ /66~ ~olut~n ~n iso--prop~lmyri~ta~e/ , ' ! 6~5 g~
P~lyo~yethylene-~orbitane~oleate . I.6 g.
.
~ 6 - 3~ -Pol~oxye~hyl~ne-~orblt~ne-m~nol~uralt~ 005 ~.
So:rbitan~ m~nol~urate 0~5 g.
I~opropanol l~O ml.
Propyl~ne ~1~col 0~4 ml.
~ylene : lO.O ml.
~ 3ba~L5DL ~ Il~L~er~ iWP/
/S~ 90 ~3};11~1p~ 6~
r ~ e 4l 2-/Z t -H~dro~y~39-tert~butyl-5 t -methyl-phon~rl/-5-ohlorobenzotri~æole ~partiol0 ~iæ~: below ~/um./ 50 %
: ~ H~ghl,~ di3p~rse ~liclo~acid /Durosil, Sup;er~il, Aeros~ etc~/ 2Q %
aol~n~ 5 %
HOE~S 1880 /1loech3t; sodlum ~alt o~
all~hatic ~u~onic acid/ ~ 2 %
:HOE;~ 19~8~/Mo~chst; ~a~ty ~lcohol polJ-~1~GQ1eth~r / . .3 ~0 . ~ ~ 100 %
, . .
E
2-/2 9 -Hyaroxy-3 ~, 5'-d~-t~r~Obutylphenyl~
5-chlorobenzotrla~o~le /particIe si~e: .
~bel~ 5/um./ 50 %
Kaoline 33 %
* '~ra I Q ~l~rl<
3~ 632~Z
~yghly di~peræe ~llolc ac~ d J.Duro~il, Sup~r~il., Aero~il3 etc./ 10 %
.~ .
HO:E S 1880 J:Hoech~-t; ~od~ al~ of an al~ph~tic ~ul:~onic acldf 2 %
HOI: S 1998 ~Hoeohs~; fatt~y alcohol poly-e~yoolethex~/ ' ~00 %
.~ , 2,,5,a-~riiphe~yl/-trl~ tri~zolo/a,c,e~-bo~zene /particle ~iz~: below 5/um. / 50 %
Highly d~per~e ~ilioic acia /~u~09il, 5uper~il, Aerosil" ~tc.~ 12 %
Kaoline . ~9 %
Sapogenst ~-180 /Hoechst; tributyl-phenol pol~31ycolether~ 7 %
q'ylose H 20 tHoechst; ` hyaro~:yethyl oal~ul:o~oJ
100 %
' 2 9 5 " B-~ri/dirlitrophenyl~tri -v-triazolo~
be~zene /pfl.r~icle ~ize ~ below 5~ / 40 %
H~ghly~ di~per~e ~ilicic aci~ /Duro~ll, :
Super~ erosil~ ~tG./ 40 %
Eaollne 10 %
Sapogen~t T-180 ~Hoeoh~; tr~butyl-Tr~e ,n1~rl~ ~
6~2 - 3~ _ phenyl pol~lycoleth~r/ l7 %
ylo~e T~180 ~.Hoec~b~ hydrox~eth~l c~llulo~e ' 100 %
~3~R~ ' Ti~a~ium dioxide ~part~cle ~ize: below 5/um:./ . 90 %
Ga~ac ~M 710 ~A~ Corp.~ 2 %
Trl~thano~m~ne I %
Poly~inylpyrrolidone K-90 /GA~ Corp~/ 2 %
H~ghl~ di~p~rse ~ilica gal iA~ro~il, Du~ Super~ etc./ .
}00~;
: ~ : ~x~m - 2 /2'~H~droxy-5~-m~thylphenyl~-benzo~r~
a~ol~/parti¢1~ size~ below 5 ~ .~ 50 ~
Hl~hly di~per~ sillc~ gsl /A~ 9 Duro~ 5uper~ - 30 %
Kaoli~e . 15 ~o ~ , . .
EOE la80 /Hoech~t9 sodlum ~alb o~
~lipha~c æul~o~ic acid~
~HOE 1998 /Eoeoh~t; ~atty ~lcohol pol~-gl~olether~ ~ 2 %
T~lo~e H~ ~0 /Hvech~:t; hy~roxyeth~l ae11ulo~e~
;~ Tr~d~
_ ~ 37 ~ 2 , ; E~ample ~7 2-~2P~-Hydroxy-5'-n-oo~ylph~nyl/-benzotri-~oL~ /par~icle ~ea~below S/um~ 50 %
B ~ - Hi~hly ~p~r~e s~llo~ eel /Aero~
Duro~ S~per~ 30 %
~Kaolin~ . 15 %
I10~ la~o ~Hoechst; sodium ~al~ o~ an àliphatic 8ulfoniG ~Rcid/ ~ ~ 2 %
OE ~998 /Hoech~-t; :~à~ty alGo~ol pol~
coleth~ 2 %
ylo~e ~I 20`/E~ech~ ydro~yethyl o~llulose/ ~ ~ 1 %
"~ ' 100 %: :
re~ni~ tesb~
Th~ compo~ s cont~i.ning ths acti~e: a~e-~t~
be~d in Table~l below:were tested on 10 applee each of the "JonQthan" 9`~"Jonared" and t'Starkin~" ~a~ieties.
The~pple were in~ler~ed~or l minu~e~into à ~pray liquid ~: ~ Gont~ning ~0.2 % by we~l~ht o~ the light~protective agent oonc~rn~d, and then.~ried at roo:m temperat:urea:
he apples were~expos~ed~bo:a mercury lamp /type~:~Tung~r~m Germicid F; waveleng~h ran~e:~l85~57a nm; dl~tance: 40 cm/
and yrere~ir~adiated ~or 4:ho~lr~s. The apple~ w~re s~ored~
~or~2:mo~ths: at +4C9 together wit~ 100 non-i~radiated ,: ~:
:
, .; , , . ~ .. .. . .. . . ..
6~2 `: `
~p~les àpplied as control:~, an~ then ~h~ re~ul~.q were ~ , ev~lu~t~d~
b r ~o~po~pple ~i~h~-protective agent`
E~ample/E~tion/ ~ariety Jonathan ~ Zs4-Dihydroxyben~ophenone~
49~ 2`~ ~ Jona:~han 2,2 D -Dihydro~y~4~4~d~-:
` methox~ben~opl1onone ; 50~ ~ ~9~ Jona~h~ ~2:,2'-Dihydro~ 4~~di-.: , : meth~xybenzophenone~5 ulf~iG acid sodiur~l 3al~
:;, ~; : , . . :
`:51 11 Jonathan 2-~dro~y-4-m~tho~ybenzo-phe~o~e-5-~sulfo~ic acid :
5~ . 13~ ~Jonathan 212~ 4~-~etrah~r~rox~-benzo~phenone ~ :
3:~:~ 15` Jo~atha~ 2-Hydroxy-~-m~tho~ybenzo-phenone ~5~ : 29~ - :Jonathan ~2-Hyd~oxy-4-n~octyloxy~
o~&ra~ benzophenone ::
: Starking :
;~55~ ~41 Jonat~an 2-~2~-Hyd~oxy-3'-tart, o~ared butyl-5-me~h~lp~enyl/-5-~ S~tarki.ng -ohlo~o~enæot~ia~ole :~5~ 42 Jo~athan 2~f2~-~Iydrox~-3~5~-d~-. Jo~red : -te~but~lp~enyl/-5- :
S:~arking -ehlor~obenzot~iazol~-`57 ~ : 43 Jo~atha~ `~,53~tri/Dhenyl~-tri-v--triazolo/~c,~/b~nz~ne ~58~ 44 Jo~atnan 2,5,8-tri/di.~itrophenyl~
tri-v-~riazolo/a,c~e/r-benzene :;, . .
.
2~
~5~
NQ of ~ompo- l~pple I~:~.ght~prol;ective ~ger E.xnm 1~ t~on v~ri.~t,y P ~I~JX~rNO" j 59 18 J~n~th~ I:~;h~ylhQxy:L 1 " 1 ' ~tli phe~g~
Jonar~3~ -~cr;ylonit;~.~il~te Starki.ng - 19 Jon~th~ lle-khyl -cyarlo~ -methyl Jo~!re~ me t,ho~;ycinn~m~l-te . ~ St~rl~i~g 61 2:1 Jonathan 5-J3, 3-Dimcthy3.-2 ~:LOX'-Jonared born~litlen~ pt;~ntene-~ e~rk:i.n~ o~
62 2~ Jonath~l /2"2'-~'hiob~4~tert.oct~
Jon~red pheno:La l;~/J-:~-bu-tylamin~-Star~clng -ni.ckel/II,I' 63 ~ ~ 25 Jor~.atha~ ck~ b3.~oc l,ylp~lellyl-Jo~ared ~;uli~itl{~ :
S~a~ki.n~ `
~ 64 ~ 26 Jonath~n Nickel~:bii~oc~ylphe~iyrl-~
:~ ~ Jv~ared~ sulfid~
- . : Starki.n~
: 65 ~20 Jonathall 5~/3~3-.~imethyl~2-nor ::: Jonared : born~lideneJ-3-pHntene~2-. 5t :Lrking : -olle 66 ~5 .lonath~n - Jonared Zinc o:gide - : S~nrking :67 ; 45: 30n~t}:~aIl : Jo~aret~ Titaniwn tlio~ide St~king Renults o:~ ~he ~raluation ~re su~ari7,ed ~ the following ~: Table ~ .
~l O ~ O ~ ~ ODlp~ L ~ i orl i~u~ o ~ ?"1_ ~p~ o l_, ~p"~
mp:Le~iiJ~ / Jo~3a-t:~in .. lon~l,r~ f:~k.lr 58 ~ 5 5~ r; 11~ _ G3 ~5 10 r~ .
G5 2~) 2 66 S 2 ~ ~
~7 ` 45 3 u~-t:r~3.ted cont:rol 10 1.0 3 ~ the abovo l;ablo clhow~3 ~ o~ tha compo~i-ti o tho 5/3~ 3 d:lme th;~ 2-1lor~ol~ly:l.iden~ ponteno-2-one9 a~
vvell a~ -tho;~e ~corltainirl~ zinc o~:id~ !~ntl ~itQlium o:~ide ~r~ the mo~t ac-~:lve in p:reventing apple p~el ~3pot.
d ~e~
6~3 h'ive ~roup~ con,~Jist.iln~ o~ two L0 year old apple troea /variety: "Jonathsn"" gra:l~ted onto M I~ subJocts /~3elec-l;ed in E`~s~ Mallin~;/ w~r0 ~o~k-~prayer wlt~l 5 litro.s e~ch o:~ ~p~y ~olutioi~.3 cont~ir~ g 0~,1 ',0 by w~i~t o:~ polyoxyethyl~7le-aorbitan~3 mollolQu:r~to /~een 20i~ 0~'05 'lo b~y weight of tolu~3n~ ~nd 0~1 p (:~.2 ~ 0"~
or lo~O % by we:Lght7 re~pec~ively9 o~' 5~3~dirno-thyl-2 orbornylid~Qe~/-3-pen-l;ene~ e ~ 24 d~y~ ho:~ore ha~ t ~rdd~. m:~rlC
~ the weathe~ condit~on~ were favollrable, ~he apple~
were harvested on l~-t. October, i.e rel~t-lvely late in ~ie~ o~ the Hungari~l meterolo~ical condit~ons~
'~he~e teet conditions r~ould be regarded as provoc~tive ~inoe the meterologic~l condltion~ had peel ~pot ~ormation~
'~he ~ruits were gathe~ed in a Y~ay that the apple~ gro~ on the pairs o~ tree~ -tre~ted with the s~me epray liquid /about 180 kg. per treeJ were collected into ~eparate container~ hereafter, aver-~ge ~amples were taken ~rom -the con~ainer~ about 200 apple~ eaoh wexe placed into apple boxe~ o~ "Szabolc3"
bype~ and the boxee were put into a cold storc~e of 4a temperature o~ the da~ o~ harv3 t.
~ No peel ~pot could be obser~ed on th~ day o~
harve~tO ~ccording to our experience~ the apples gath-ered from the epra~ed tree~ were more evenly and more uni~o~mly coloured than those grown o~ the untrea~-ed controls.
At the end o~ the ~torage~period, i.e. a~t~r 5 months, the extent o~ peel ~potting ~nd the storage los~ /number o~ rotten applee/ were determined.
~ The~result~ are summarized in '~able 2 1~2 ~ 2 T~ble 2 concentr~lOrL ~ Df appl~
of the spr~y . M~LY P~e1 1 or - liquid/w/w ~O/ ~o~al Rotten spots p~ po~
` ~0~1 202 15 ~~ 31 2 ~12 12 ~ 19 0~l4 1~35 13 0~ 6 197 11 - 5 lo 0 210 14 ~
O !corLtrol/ 241 19 6~ l~
O /control/ 443 23 119 ~ appears ~rom ~he data of ~able~2 that~
the developme~Lt~o~ peol spo~s was completely ~liminated or~at lesst reduced to the minimum upon u~ing the method and compo~ition~ accord~rLg~to the inverLtion.
.
.
he e~periments per~orm~:d in the ~lo ye~r .
wi~h oomposition~ contài~ing c~lcîum ~aIts /~ee HuxLgar-i~n Pa~ent No, 159,~199/ on the ~amo or di~'erent ~oll~
havo ~hown ~ protection o~ only 10 to 30 ~O~
~,xa,mE__ 6~ .
One proceeds exactly a~ de~crib0d in Example :68 wi~h the ~ erence that -~h~ apple trees are sprayed , .
Z6~;~
,~tw~L~e wi~h a ~3pra;y ~ol~ Lon con~alrling lelO % by wQight o~ 5-~3, 3-dimethyl~2-~1orborrl~rlldene/-3~pen~e^~
llO~~-QXI~ ,' 'L'he ~eoon~l ~px~yi~ per:Eo~ ed one weffk ~:~ ter the :~irs t ~
'l'he re~3ult~ are ~umm~ri~ed in Table 4!, The dat~ o~ Ta~le cl i~dicate tha t X10 prs,c-~ical advan~aees ari~ :Erom doubl~ ,spra;yin~O ~h~ peel spo t3 / 1 to 2 ~pots oll 3 ~ ~pple~/ ob3er~ed after ~ .
ouble ispr~ying a:re u~ithin the error limi~
:
T~ble 4 ii NllDl~r E~n~l ~ ,~
d~te OI ~ I~
~pra~Jing'L'otal Rot~erl ~poti~ pee~ ~pots o ~coll~rolf~4~ 6 . ~SRP ~
c~ontrol/~ 210 14 X: :/~i~p~ ~d p~ lf 185 17 ~ 3 0 fco:nbrol~ 3 23 ~ ::119 . ~ : :
. - 3~1a~
One proceeds exActl~ a~q de~c~ibis(l i~ .~mpl~
. . .
6i~ wi~h ths d;l:E~erens~e ~ha t di~3alloyl trloleate: ~ ~
~pplied ~ aG~ive~ a~ell~, The spra~ quid cont~in9 0~'1%
by w~ight :o:~ acti~e a~;ent? Oo~l % b~r: wei~ht o:f pol~ro~
Qthy10rle ~orbitane i monola~ a te /'L'~veen 20~ and 0,~05 i;' . b~r w~ o~ tolue.~e. '.~he re~ul~s are summar:ized in blo~ 5 i~d ~ 9' 6~2 .
;
oi 1 40 O o n, ~ c~
~s a~ ~ d C~ r-l Cq rl r~\ ~D
r-l C¦ (\I tV .~ ~ ~ ~
.' ~e)o ~'0~ ~; O
~IJ 4 , ~ O r-l ~ ca CQ C.~ C~ hD O ~
C~) ~1 1 ~ O a~
'~ O f~
~ I t ~ r~ O ~Oq~ ~15 ~ 3 0 ~1 ~0 ~ , a: ~ ~
~D J~ a tl) ~ r~ r~
~1 ~ o El ~ r~ ~D
~ 0 0 (fl ~ ~
rl r tq : C
~$ ~ hD O
o~ ~ h ~ ~ O
~ c~
~ ~O ~ CO ~
,q C~ I r-l r~ ~
r~ r ~1 O P~
.Q ~ f~, ~I h ~ ~
U) 13 ~ rC! æ O
c~ h f~ ~ .
-l r~
C) O r~lC) O
s ~ Z~i9 . , ;
.. . . .. . _ __ . --.. , . . _ b~ Numb~.r ~ 3 , spra~:LIle ~o .,~ 0 spc) t.c~ peel ~tpot;~3 ~: `
: O ~control~ ~3 23 1.19 - ~
~3 10 1~6 :: ~3X~IIP1~2`: 71 ` ~0 ~
____ .
On~ p-rooe~3 ~e~ I.y ~AcJ de3cribed :ln ~ ~nple 6~ w~th~ the di~`f'~r~ o~ th~lt ~he æpray ~301u~.~on~ p:r~p~r-e~ :~rom thc oompo~ on~ ll.st~.~cl :i.n 'T~ ble 7 are u,~ed ~o .: , -3pr~y ~roup~q con.~3i~l t:~ng Q~ 2 ~Ipple tr~es.
,~ .... Compor~
N~be~ o:E ~ tion ` ~:
:~.U}~mpl~ 3x,,.1~o./ ro~eo~iv~ ellt :~ 71 -~ 3 : ~5,l~ 59,ll'~Di~le~ydrobenzo- :
: . : ~riclY~ o /2'9l-~_/be~zotrl~zcle .
7~ 5 : ~J:i~ c o:~lde /pnrtiçle .size:
t-73 6 ~ Zinr~ oxide /p~rticl~ size:
b~low~5~un~ cl 2-/2~-hydr-ox~-3~-~er~ utyl-53-meth~l - phenyl~-~-chlo~obe~zotri~zole :~ 74 ; - ~`l2 ~2-~rdroxy-4-me~-ho~berlzopll~one-5-,qu~ on:ic ~G:Ld and 2~2' ,4,45-tetr~h~drc~ybe1lzoph~llone 75 ~ ` 17 ~2-~tll~l.he~ d.Lphe~yl-u~rylonit~ilate ~76 ~ /2,2'-'l'hiob~3/~-ter-t~cct~l-. p.henol~te~/-n~ mi : ~i.ckel ~II/
.
2~2 77 251 2-IIyd~ro~ ootylc~ ;y~ sophe~o~e 7~ J2;~ ty~lrc~cy-3~ ~dl~ o^~
buitylp~l~yl~ ohlo~b~rlssotrie~qsole a~d niok~l~bl~ootylph~n~ ul~id~3 7~? 3~5 2~ 2 ~ ~.~dro~r~3 ~ dl~t~r ~ -ylphe~y~ hl~ sb~ .otr:ia2:01e ~d /~ ~, 2 ' ~liO~3~ OO~Y1-D
37 2~h l;ylhs~ d~ph~ aorylo anCI 2~2~-~h~ (4-~r~.-p~ R~ u l;y.~a~:~a-~cskel ~ XI) 81 ~!~ N:l.ot~e:L~b:L~30~ k3,~1ph~5~y3. ~ul~lde ,~r~3r~
82 26 ~lolEel-bl~oo~ylplle~yl ~ul~ide ~rro I~M~
83 31 Nickal ~1~oo1tylph~ ul~Lda a~ 5 -~3~ 3~d~.me~lyl~2~or~or~yl-:~de ~3~pe~te one ; B4 ~ 4 ~ -/3 ~ 3~ Jl~ ~Q~or~l~
p~ on~
~rom the oompo~ t.iOlI~3 ment:l.oile~ ~ t~e aboYe Exa~npl~Y
~pray BOllltlO~ 3 oont;~.~ln~ ; 0 j2 ~ ~ by wei~;ht o~ ~3o~e ~ent we~0 preparl3d~ . ~he app~e ~ree~ wl3re ~pra~ed orL
8th Septem~erq, ~e apple~3 were ~sa*h~ed on 8th Ootober t~e~ 100-20~:) ra~do~ly s~leet~d ~pl~ per treat~e~t we~o ~tored at 1~ ~C tlll 313t Ja~uary. ~ext year, The e:~t~ o~ pe~ ~pot~ g wa3 ~et~i~ed v~ 18~ ~bruary~, ~3~ult~ o~ ~he e~v~luatiorl are ~u~mariLæed 1:D
T~bl~ 8a ~ ~
.
~;269~2 Table 8 _ Number of a~ples_ _ _ No. of Composi- Total Without 1. or 2 many No. of apples :. Exan~ple tion spot peel peel without spot in /Ex. No/ spots spots ~ of the total untreated control 385 73 181 131 18,9 72 5 127 104 23 - 8~,0 ~ 73 6 128 ~8 36 3 68,0 : 7~ 12 132 67 ~8 17 5~,0 83 31 145 87 51 7 60,0 8~ 40 118 98 14 16 83,0 ~'
pe~t~ne-2-on~ : 3.05 g.
Polyoxy~t~y1sne-~orb~tane-o1~te 1.0 Polyo~hyl~na-~sorb1~ane-8t~arat~ 0,.5 ~-Sorb~a~e stear~e ; ~ 0 . 5 g o ~yle~e~
~,, . ~ ~. . . -/2 j 2 "-T~obis-J4 i;~*t, o~tylpl~enc~late//-butyla~n1n~-nlck~l~ JI~ - 2 ~;0 l!~o}~T~pli~ol pol~gl~o~hor /;~Q 10/ - 108 g~
.
10.O ml.
_ 29 ~ ' ]:~ enple 2~
Nic.ke~bi~octylphenyl ~ulfid:e /FerrQ
~M 3.01; Per~o Chomical / 2 e~
~ Nollylphenol p~ly~lycoleth~r ~0 10/ 1~8 ~.
: ~ ~yl~n~
lO~O ml.
Nickel-bi~ootylphenyl ~ulfide /~er~o A~1~105; ~e~ro Gh~mical/ 2 g.
Nonylphenol poly~lyoole~her /~0 10/ : 1~8 ~.
Xylane .
10.0 ml~: :
; . : ~ ~
e~orcinol monoben30a~e ~ 2 g~:
No~ylphenol polyglycole~her ~E0~0 i l.O g~
:~:Sorb:itane trioleab~ ~ 0.5~g.
~Polyoxye~hyle~e-~o~rbit~ne-oleate ~ ~ 0.5 g.
Ethyl acetat~ ~5 ml.
Xyl:ene ~ : 2.5 m,l.
~ lO.O ml~
",, ~ xam~
- Di~alloyl trioleate- ~ ~ 2 g~
.. . .
~onylphenol polygl~Goleth~r jEO~10J . . 1.5 g.
i ~Sorbitane triolea~e ~ : 0.5 e-:X~l~n~
10.0 ml~
.
. . ~ . .", . - , ~ .
2~2 o~y-~-n-octylo5~yb~1nzQl?he~lone ga No~yIphenol polyglycolether /E0 10~ 1.5 g.
NonyrlphenoI poly~lycol~ther ~0 4-6/ ` 0.5 g~
~yle~ L;~
lV.0 m~0 _~e~ 0 2~Ethylhexyl I,I'-diphenyl~Qcrylonitrilato I.'5 g~
2-Hydro~y~-me~ho~JbeIlzophenone : 0~5 g Non~].phenol polyglycolether /E0 10~ 1.5 g~
~ylene 7.~ml.
. .
~ : 10~0 ml.
66 ~o I~oprop~rlmgri~tate solution o~ 5~
: ~-f~3-dimeth~1-2-norbornyliden~/-3-pe~t-~ ~ ene-2-one ~ 1.5 g.
.
Nickel-bisootylphenyl ~uIfide t~erro 0~ e~ro ~hemO~ g.
Nonylphenol polyglycolether ~0 lOJ 1 gg' atty alcohol polyelycoIether ~ 0~ g.
Polyoxyeth~lene~orbi~ane-~r~oleate 0,5 g.
Xylene :10~ ml~
- ~ 2-~thylhe~yl 1?1~ -diphenyl-acrylonitril~t~ 1 gO
.
~ 3.~ 6~
2~ droxy~4~m~ho:~rbenzophenone 1 ~, Nonylphenol po~yglyooleth~ /EO lOf 0.5 ~a~-ty ~lc~hol po:Ly~lycolether 0.5 g~
Polyoxyethylen~-cJ~orb:itanç3-trloleate 1 g,.
Xylerle 10~0 ml.
~e~
2~Ethylhexyl 1, 1 7 -dlphenyl~acrylon~trilab~ 1 g.
.
2-Hydro~y~4-n-oct,ylo}:ybenzQphenone 1 ~;.
Nonylpheno:l poly~lyoolether /EO 10/ 0,5 atty alcohol po:Ly~lycole~her ^ 0.5 g~
Polyoxyebhylene~sorbi.tan~-~rio-eate 1 e:~
Xylene 10~0 ml~-~pl~
Nick01~bi~0c-tylphen~l sul~lde /Ferro AM-101; Ferro ChemO/ 1~6 g~
2-/2~'Hydroxy-3~5'-di-tert.butylphenyl/-~5~chlorobenzo~rlazole 0~4 g.
~onylphenol polygl~cole~her JEo loJ ~5 e.
att~ alcohol polyglycole-ther 0,5 g~ -Polyoxyethylen2-~orbitan~-trioleate 1 g.
~ylen~
lOoO ml.
~ ~2fi9 - ~3~
~ie~el~bi~octylphenyl sul~d~ /~erro ~M-105~ ~rrp ChemO/ 1~6 g.
2-~29-Hy~ro~y~3 9 ~ 5'-di tert~butylphen~
-5-chlorob~zotri~o1~ 0.4 g~
~onylphenol poly~l-g¢olether ~0 10~ 0~5 g~
~tty alcohol poly~lyco~ther 0.5 ~.
:! .
Polyox~thylene~sorbitan~-t~iQle~te 1 g.
~;yle:n~ ~
10 mlO
i /2 9 2'~Thiobi~-/4-t~-t.ootylphe~olate~ n~
bubylamino-niokel~ 6 g, 2-~2~-Hydro~y-3 t ~ 5 ~ -di~tert~but~lphenyl~
-5-chlorob~nzotr-l:azole . ~ 0.4 g.
No~ylphenol polyglycoleth~r 0.5 g~
~at:ty alcohol poly~lycolether 0.5 P~lyo~yethylene-~orbitan~-trioloate 1 g~:
gy1en~
' 10 ml9 2-Ethylhexyl I 7 19 -d~phen~l-acrylonitril~te 1 g.
2~/2~-Th~vbi~-/4-tert00ctylphenol~te//- .
-~ butylamine-~ickel/II/ ` 1 ~, Nonylphenol polyglycolether ~ 005 g~
, ;;
~ 6 _ 33 T~'att~ aloohol polyglycolether O.S gO
Polyoxy~th~.ene-sorbit~ne~trloleat~
~Ho~ch3t A~ 0 X~yIene 10~0 m~
5~3~3~D~methyl-2-norbo~nylidene/-3--pen~ne-2 one ~ 1~5 g.
2~Mydro~-4-n-oct~loxyb~nzophe~one 1.0 g~
Polyo~yethylene~orbltane-ol~ate 1.,0 g. ,~
Polyo~yeth~len~-~orbitane-3tearate 0.3 g~ ;
Isop~opanol 0.5 ml. :
Propylene glycol - ~ 0~5 ml i ~ylen~ ~ 5 ml. _ lO~.:ml, __ 39 ~Di~allo~l trloleate 4 g.
Polyo~yethyl~ne-sorbitane-monol~ura~e ~ g.
o~ue~ ~ ? ~
~10 g.
~ '.
5-f3~3~Dimethyl-2-norbornylide~e/~3-~penten~2-on~ /66~ ~olut~n ~n iso--prop~lmyri~ta~e/ , ' ! 6~5 g~
P~lyo~yethylene-~orbitane~oleate . I.6 g.
.
~ 6 - 3~ -Pol~oxye~hyl~ne-~orblt~ne-m~nol~uralt~ 005 ~.
So:rbitan~ m~nol~urate 0~5 g.
I~opropanol l~O ml.
Propyl~ne ~1~col 0~4 ml.
~ylene : lO.O ml.
~ 3ba~L5DL ~ Il~L~er~ iWP/
/S~ 90 ~3};11~1p~ 6~
r ~ e 4l 2-/Z t -H~dro~y~39-tert~butyl-5 t -methyl-phon~rl/-5-ohlorobenzotri~æole ~partiol0 ~iæ~: below ~/um./ 50 %
: ~ H~ghl,~ di3p~rse ~liclo~acid /Durosil, Sup;er~il, Aeros~ etc~/ 2Q %
aol~n~ 5 %
HOE~S 1880 /1loech3t; sodlum ~alt o~
all~hatic ~u~onic acid/ ~ 2 %
:HOE;~ 19~8~/Mo~chst; ~a~ty ~lcohol polJ-~1~GQ1eth~r / . .3 ~0 . ~ ~ 100 %
, . .
E
2-/2 9 -Hyaroxy-3 ~, 5'-d~-t~r~Obutylphenyl~
5-chlorobenzotrla~o~le /particIe si~e: .
~bel~ 5/um./ 50 %
Kaoline 33 %
* '~ra I Q ~l~rl<
3~ 632~Z
~yghly di~peræe ~llolc ac~ d J.Duro~il, Sup~r~il., Aero~il3 etc./ 10 %
.~ .
HO:E S 1880 J:Hoech~-t; ~od~ al~ of an al~ph~tic ~ul:~onic acldf 2 %
HOI: S 1998 ~Hoeohs~; fatt~y alcohol poly-e~yoolethex~/ ' ~00 %
.~ , 2,,5,a-~riiphe~yl/-trl~ tri~zolo/a,c,e~-bo~zene /particle ~iz~: below 5/um. / 50 %
Highly d~per~e ~ilioic acia /~u~09il, 5uper~il, Aerosil" ~tc.~ 12 %
Kaoline . ~9 %
Sapogenst ~-180 /Hoechst; tributyl-phenol pol~31ycolether~ 7 %
q'ylose H 20 tHoechst; ` hyaro~:yethyl oal~ul:o~oJ
100 %
' 2 9 5 " B-~ri/dirlitrophenyl~tri -v-triazolo~
be~zene /pfl.r~icle ~ize ~ below 5~ / 40 %
H~ghly~ di~per~e ~ilicic aci~ /Duro~ll, :
Super~ erosil~ ~tG./ 40 %
Eaollne 10 %
Sapogen~t T-180 ~Hoeoh~; tr~butyl-Tr~e ,n1~rl~ ~
6~2 - 3~ _ phenyl pol~lycoleth~r/ l7 %
ylo~e T~180 ~.Hoec~b~ hydrox~eth~l c~llulo~e ' 100 %
~3~R~ ' Ti~a~ium dioxide ~part~cle ~ize: below 5/um:./ . 90 %
Ga~ac ~M 710 ~A~ Corp.~ 2 %
Trl~thano~m~ne I %
Poly~inylpyrrolidone K-90 /GA~ Corp~/ 2 %
H~ghl~ di~p~rse ~ilica gal iA~ro~il, Du~ Super~ etc./ .
}00~;
: ~ : ~x~m - 2 /2'~H~droxy-5~-m~thylphenyl~-benzo~r~
a~ol~/parti¢1~ size~ below 5 ~ .~ 50 ~
Hl~hly di~per~ sillc~ gsl /A~ 9 Duro~ 5uper~ - 30 %
Kaoli~e . 15 ~o ~ , . .
EOE la80 /Hoech~t9 sodlum ~alb o~
~lipha~c æul~o~ic acid~
~HOE 1998 /Eoeoh~t; ~atty ~lcohol pol~-gl~olether~ ~ 2 %
T~lo~e H~ ~0 /Hvech~:t; hy~roxyeth~l ae11ulo~e~
;~ Tr~d~
_ ~ 37 ~ 2 , ; E~ample ~7 2-~2P~-Hydroxy-5'-n-oo~ylph~nyl/-benzotri-~oL~ /par~icle ~ea~below S/um~ 50 %
B ~ - Hi~hly ~p~r~e s~llo~ eel /Aero~
Duro~ S~per~ 30 %
~Kaolin~ . 15 %
I10~ la~o ~Hoechst; sodium ~al~ o~ an àliphatic 8ulfoniG ~Rcid/ ~ ~ 2 %
OE ~998 /Hoech~-t; :~à~ty alGo~ol pol~
coleth~ 2 %
ylo~e ~I 20`/E~ech~ ydro~yethyl o~llulose/ ~ ~ 1 %
"~ ' 100 %: :
re~ni~ tesb~
Th~ compo~ s cont~i.ning ths acti~e: a~e-~t~
be~d in Table~l below:were tested on 10 applee each of the "JonQthan" 9`~"Jonared" and t'Starkin~" ~a~ieties.
The~pple were in~ler~ed~or l minu~e~into à ~pray liquid ~: ~ Gont~ning ~0.2 % by we~l~ht o~ the light~protective agent oonc~rn~d, and then.~ried at roo:m temperat:urea:
he apples were~expos~ed~bo:a mercury lamp /type~:~Tung~r~m Germicid F; waveleng~h ran~e:~l85~57a nm; dl~tance: 40 cm/
and yrere~ir~adiated ~or 4:ho~lr~s. The apple~ w~re s~ored~
~or~2:mo~ths: at +4C9 together wit~ 100 non-i~radiated ,: ~:
:
, .; , , . ~ .. .. . .. . . ..
6~2 `: `
~p~les àpplied as control:~, an~ then ~h~ re~ul~.q were ~ , ev~lu~t~d~
b r ~o~po~pple ~i~h~-protective agent`
E~ample/E~tion/ ~ariety Jonathan ~ Zs4-Dihydroxyben~ophenone~
49~ 2`~ ~ Jona:~han 2,2 D -Dihydro~y~4~4~d~-:
` methox~ben~opl1onone ; 50~ ~ ~9~ Jona~h~ ~2:,2'-Dihydro~ 4~~di-.: , : meth~xybenzophenone~5 ulf~iG acid sodiur~l 3al~
:;, ~; : , . . :
`:51 11 Jonathan 2-~dro~y-4-m~tho~ybenzo-phe~o~e-5-~sulfo~ic acid :
5~ . 13~ ~Jonathan 212~ 4~-~etrah~r~rox~-benzo~phenone ~ :
3:~:~ 15` Jo~atha~ 2-Hydroxy-~-m~tho~ybenzo-phenone ~5~ : 29~ - :Jonathan ~2-Hyd~oxy-4-n~octyloxy~
o~&ra~ benzophenone ::
: Starking :
;~55~ ~41 Jonat~an 2-~2~-Hyd~oxy-3'-tart, o~ared butyl-5-me~h~lp~enyl/-5-~ S~tarki.ng -ohlo~o~enæot~ia~ole :~5~ 42 Jo~athan 2~f2~-~Iydrox~-3~5~-d~-. Jo~red : -te~but~lp~enyl/-5- :
S:~arking -ehlor~obenzot~iazol~-`57 ~ : 43 Jo~atha~ `~,53~tri/Dhenyl~-tri-v--triazolo/~c,~/b~nz~ne ~58~ 44 Jo~atnan 2,5,8-tri/di.~itrophenyl~
tri-v-~riazolo/a,c~e/r-benzene :;, . .
.
2~
~5~
NQ of ~ompo- l~pple I~:~.ght~prol;ective ~ger E.xnm 1~ t~on v~ri.~t,y P ~I~JX~rNO" j 59 18 J~n~th~ I:~;h~ylhQxy:L 1 " 1 ' ~tli phe~g~
Jonar~3~ -~cr;ylonit;~.~il~te Starki.ng - 19 Jon~th~ lle-khyl -cyarlo~ -methyl Jo~!re~ me t,ho~;ycinn~m~l-te . ~ St~rl~i~g 61 2:1 Jonathan 5-J3, 3-Dimcthy3.-2 ~:LOX'-Jonared born~litlen~ pt;~ntene-~ e~rk:i.n~ o~
62 2~ Jonath~l /2"2'-~'hiob~4~tert.oct~
Jon~red pheno:La l;~/J-:~-bu-tylamin~-Star~clng -ni.ckel/II,I' 63 ~ ~ 25 Jor~.atha~ ck~ b3.~oc l,ylp~lellyl-Jo~ared ~;uli~itl{~ :
S~a~ki.n~ `
~ 64 ~ 26 Jonath~n Nickel~:bii~oc~ylphe~iyrl-~
:~ ~ Jv~ared~ sulfid~
- . : Starki.n~
: 65 ~20 Jonathall 5~/3~3-.~imethyl~2-nor ::: Jonared : born~lideneJ-3-pHntene~2-. 5t :Lrking : -olle 66 ~5 .lonath~n - Jonared Zinc o:gide - : S~nrking :67 ; 45: 30n~t}:~aIl : Jo~aret~ Titaniwn tlio~ide St~king Renults o:~ ~he ~raluation ~re su~ari7,ed ~ the following ~: Table ~ .
~l O ~ O ~ ~ ODlp~ L ~ i orl i~u~ o ~ ?"1_ ~p~ o l_, ~p"~
mp:Le~iiJ~ / Jo~3a-t:~in .. lon~l,r~ f:~k.lr 58 ~ 5 5~ r; 11~ _ G3 ~5 10 r~ .
G5 2~) 2 66 S 2 ~ ~
~7 ` 45 3 u~-t:r~3.ted cont:rol 10 1.0 3 ~ the abovo l;ablo clhow~3 ~ o~ tha compo~i-ti o tho 5/3~ 3 d:lme th;~ 2-1lor~ol~ly:l.iden~ ponteno-2-one9 a~
vvell a~ -tho;~e ~corltainirl~ zinc o~:id~ !~ntl ~itQlium o:~ide ~r~ the mo~t ac-~:lve in p:reventing apple p~el ~3pot.
d ~e~
6~3 h'ive ~roup~ con,~Jist.iln~ o~ two L0 year old apple troea /variety: "Jonathsn"" gra:l~ted onto M I~ subJocts /~3elec-l;ed in E`~s~ Mallin~;/ w~r0 ~o~k-~prayer wlt~l 5 litro.s e~ch o:~ ~p~y ~olutioi~.3 cont~ir~ g 0~,1 ',0 by w~i~t o:~ polyoxyethyl~7le-aorbitan~3 mollolQu:r~to /~een 20i~ 0~'05 'lo b~y weight of tolu~3n~ ~nd 0~1 p (:~.2 ~ 0"~
or lo~O % by we:Lght7 re~pec~ively9 o~' 5~3~dirno-thyl-2 orbornylid~Qe~/-3-pen-l;ene~ e ~ 24 d~y~ ho:~ore ha~ t ~rdd~. m:~rlC
~ the weathe~ condit~on~ were favollrable, ~he apple~
were harvested on l~-t. October, i.e rel~t-lvely late in ~ie~ o~ the Hungari~l meterolo~ical condit~ons~
'~he~e teet conditions r~ould be regarded as provoc~tive ~inoe the meterologic~l condltion~ had peel ~pot ~ormation~
'~he ~ruits were gathe~ed in a Y~ay that the apple~ gro~ on the pairs o~ tree~ -tre~ted with the s~me epray liquid /about 180 kg. per treeJ were collected into ~eparate container~ hereafter, aver-~ge ~amples were taken ~rom -the con~ainer~ about 200 apple~ eaoh wexe placed into apple boxe~ o~ "Szabolc3"
bype~ and the boxee were put into a cold storc~e of 4a temperature o~ the da~ o~ harv3 t.
~ No peel ~pot could be obser~ed on th~ day o~
harve~tO ~ccording to our experience~ the apples gath-ered from the epra~ed tree~ were more evenly and more uni~o~mly coloured than those grown o~ the untrea~-ed controls.
At the end o~ the ~torage~period, i.e. a~t~r 5 months, the extent o~ peel ~potting ~nd the storage los~ /number o~ rotten applee/ were determined.
~ The~result~ are summarized in '~able 2 1~2 ~ 2 T~ble 2 concentr~lOrL ~ Df appl~
of the spr~y . M~LY P~e1 1 or - liquid/w/w ~O/ ~o~al Rotten spots p~ po~
` ~0~1 202 15 ~~ 31 2 ~12 12 ~ 19 0~l4 1~35 13 0~ 6 197 11 - 5 lo 0 210 14 ~
O !corLtrol/ 241 19 6~ l~
O /control/ 443 23 119 ~ appears ~rom ~he data of ~able~2 that~
the developme~Lt~o~ peol spo~s was completely ~liminated or~at lesst reduced to the minimum upon u~ing the method and compo~ition~ accord~rLg~to the inverLtion.
.
.
he e~periments per~orm~:d in the ~lo ye~r .
wi~h oomposition~ contài~ing c~lcîum ~aIts /~ee HuxLgar-i~n Pa~ent No, 159,~199/ on the ~amo or di~'erent ~oll~
havo ~hown ~ protection o~ only 10 to 30 ~O~
~,xa,mE__ 6~ .
One proceeds exactly a~ de~crib0d in Example :68 wi~h the ~ erence that -~h~ apple trees are sprayed , .
Z6~;~
,~tw~L~e wi~h a ~3pra;y ~ol~ Lon con~alrling lelO % by wQight o~ 5-~3, 3-dimethyl~2-~1orborrl~rlldene/-3~pen~e^~
llO~~-QXI~ ,' 'L'he ~eoon~l ~px~yi~ per:Eo~ ed one weffk ~:~ ter the :~irs t ~
'l'he re~3ult~ are ~umm~ri~ed in Table 4!, The dat~ o~ Ta~le cl i~dicate tha t X10 prs,c-~ical advan~aees ari~ :Erom doubl~ ,spra;yin~O ~h~ peel spo t3 / 1 to 2 ~pots oll 3 ~ ~pple~/ ob3er~ed after ~ .
ouble ispr~ying a:re u~ithin the error limi~
:
T~ble 4 ii NllDl~r E~n~l ~ ,~
d~te OI ~ I~
~pra~Jing'L'otal Rot~erl ~poti~ pee~ ~pots o ~coll~rolf~4~ 6 . ~SRP ~
c~ontrol/~ 210 14 X: :/~i~p~ ~d p~ lf 185 17 ~ 3 0 fco:nbrol~ 3 23 ~ ::119 . ~ : :
. - 3~1a~
One proceeds exActl~ a~q de~c~ibis(l i~ .~mpl~
. . .
6i~ wi~h ths d;l:E~erens~e ~ha t di~3alloyl trloleate: ~ ~
~pplied ~ aG~ive~ a~ell~, The spra~ quid cont~in9 0~'1%
by w~ight :o:~ acti~e a~;ent? Oo~l % b~r: wei~ht o:f pol~ro~
Qthy10rle ~orbitane i monola~ a te /'L'~veen 20~ and 0,~05 i;' . b~r w~ o~ tolue.~e. '.~he re~ul~s are summar:ized in blo~ 5 i~d ~ 9' 6~2 .
;
oi 1 40 O o n, ~ c~
~s a~ ~ d C~ r-l Cq rl r~\ ~D
r-l C¦ (\I tV .~ ~ ~ ~
.' ~e)o ~'0~ ~; O
~IJ 4 , ~ O r-l ~ ca CQ C.~ C~ hD O ~
C~) ~1 1 ~ O a~
'~ O f~
~ I t ~ r~ O ~Oq~ ~15 ~ 3 0 ~1 ~0 ~ , a: ~ ~
~D J~ a tl) ~ r~ r~
~1 ~ o El ~ r~ ~D
~ 0 0 (fl ~ ~
rl r tq : C
~$ ~ hD O
o~ ~ h ~ ~ O
~ c~
~ ~O ~ CO ~
,q C~ I r-l r~ ~
r~ r ~1 O P~
.Q ~ f~, ~I h ~ ~
U) 13 ~ rC! æ O
c~ h f~ ~ .
-l r~
C) O r~lC) O
s ~ Z~i9 . , ;
.. . . .. . _ __ . --.. , . . _ b~ Numb~.r ~ 3 , spra~:LIle ~o .,~ 0 spc) t.c~ peel ~tpot;~3 ~: `
: O ~control~ ~3 23 1.19 - ~
~3 10 1~6 :: ~3X~IIP1~2`: 71 ` ~0 ~
____ .
On~ p-rooe~3 ~e~ I.y ~AcJ de3cribed :ln ~ ~nple 6~ w~th~ the di~`f'~r~ o~ th~lt ~he æpray ~301u~.~on~ p:r~p~r-e~ :~rom thc oompo~ on~ ll.st~.~cl :i.n 'T~ ble 7 are u,~ed ~o .: , -3pr~y ~roup~q con.~3i~l t:~ng Q~ 2 ~Ipple tr~es.
,~ .... Compor~
N~be~ o:E ~ tion ` ~:
:~.U}~mpl~ 3x,,.1~o./ ro~eo~iv~ ellt :~ 71 -~ 3 : ~5,l~ 59,ll'~Di~le~ydrobenzo- :
: . : ~riclY~ o /2'9l-~_/be~zotrl~zcle .
7~ 5 : ~J:i~ c o:~lde /pnrtiçle .size:
t-73 6 ~ Zinr~ oxide /p~rticl~ size:
b~low~5~un~ cl 2-/2~-hydr-ox~-3~-~er~ utyl-53-meth~l - phenyl~-~-chlo~obe~zotri~zole :~ 74 ; - ~`l2 ~2-~rdroxy-4-me~-ho~berlzopll~one-5-,qu~ on:ic ~G:Ld and 2~2' ,4,45-tetr~h~drc~ybe1lzoph~llone 75 ~ ` 17 ~2-~tll~l.he~ d.Lphe~yl-u~rylonit~ilate ~76 ~ /2,2'-'l'hiob~3/~-ter-t~cct~l-. p.henol~te~/-n~ mi : ~i.ckel ~II/
.
2~2 77 251 2-IIyd~ro~ ootylc~ ;y~ sophe~o~e 7~ J2;~ ty~lrc~cy-3~ ~dl~ o^~
buitylp~l~yl~ ohlo~b~rlssotrie~qsole a~d niok~l~bl~ootylph~n~ ul~id~3 7~? 3~5 2~ 2 ~ ~.~dro~r~3 ~ dl~t~r ~ -ylphe~y~ hl~ sb~ .otr:ia2:01e ~d /~ ~, 2 ' ~liO~3~ OO~Y1-D
37 2~h l;ylhs~ d~ph~ aorylo anCI 2~2~-~h~ (4-~r~.-p~ R~ u l;y.~a~:~a-~cskel ~ XI) 81 ~!~ N:l.ot~e:L~b:L~30~ k3,~1ph~5~y3. ~ul~lde ,~r~3r~
82 26 ~lolEel-bl~oo~ylplle~yl ~ul~ide ~rro I~M~
83 31 Nickal ~1~oo1tylph~ ul~Lda a~ 5 -~3~ 3~d~.me~lyl~2~or~or~yl-:~de ~3~pe~te one ; B4 ~ 4 ~ -/3 ~ 3~ Jl~ ~Q~or~l~
p~ on~
~rom the oompo~ t.iOlI~3 ment:l.oile~ ~ t~e aboYe Exa~npl~Y
~pray BOllltlO~ 3 oont;~.~ln~ ; 0 j2 ~ ~ by wei~;ht o~ ~3o~e ~ent we~0 preparl3d~ . ~he app~e ~ree~ wl3re ~pra~ed orL
8th Septem~erq, ~e apple~3 were ~sa*h~ed on 8th Ootober t~e~ 100-20~:) ra~do~ly s~leet~d ~pl~ per treat~e~t we~o ~tored at 1~ ~C tlll 313t Ja~uary. ~ext year, The e:~t~ o~ pe~ ~pot~ g wa3 ~et~i~ed v~ 18~ ~bruary~, ~3~ult~ o~ ~he e~v~luatiorl are ~u~mariLæed 1:D
T~bl~ 8a ~ ~
.
~;269~2 Table 8 _ Number of a~ples_ _ _ No. of Composi- Total Without 1. or 2 many No. of apples :. Exan~ple tion spot peel peel without spot in /Ex. No/ spots spots ~ of the total untreated control 385 73 181 131 18,9 72 5 127 104 23 - 8~,0 ~ 73 6 128 ~8 36 3 68,0 : 7~ 12 132 67 ~8 17 5~,0 83 31 145 87 51 7 60,0 8~ 40 118 98 14 16 83,0 ~'
Claims (43)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composition for the prophylaxis of apple peel spot which comprises at least one light-protective agent together with a carrier, diluent or other auxiliary agent useful in plant-protecting compositions and at least one other biologically active substance.
2. A composition for the prophylaxis of "Jonathan" peel spot, which contains 0.05 to 99.5% by weight of at least one UV-absorber together with a carrier, diluent or other auxiliary agent useful in plant-protecting compositions and at least one other biologically active substance.
3. A composition as claimed in claim 1, which contains one or more light screeners, quenchers, radical scavengers or peroxide decomposers as light-protective agent.
4. A composition as claimed in claim 1, which contains at least one light screener as light-protective agent.
5. A composition as claimed in claim 1, which contains at least one quencher as light-protective agent.
6. A composition as claimed in claim 1, which contains at least one radical scavenger or peroxide decomposer as light-protective agent.
7. A composition as claimed in claim 1 which contains zinc oxide or titanium dioxide or both zinc oxide and titanium dioxide as light-protective agent.
8. A composition as claimed in claim 1, 2 or 3 which contains at least one light-protective agent selected from benzo-phenone derivatives, benzotriazole derivatives, dibenzotriazole derivatives, tris-triazolobenzene derivatives, aromatic ester derivatives, substituted acrylonitrile derivatives, metalorganic compounds and alicyclic dienone derivatives.
9. A composition as claimed in claim 1, 2 or 3 which contains at least one light-protective agent selected from 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxy-benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sulfonic acid sodium salt, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-heptyloxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 5-sulfonic acid and 2-hydroxy-2'-chlorobenzophenone.
10. A composition as claimed in claim 1, 2 or 3 which contains at least one light-protective agent selected from 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(2'-hydroxy-5'-n-octylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert.butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert.butyl-5'-methylphenyl)-5-chlorobenzotriazole and 5,11H-5',11' didehydrobenzotriazolo[2',1-a] benzotriazole.
11. A composition as claimed in claim 1, 2 or 3 which contains at least one light-protective group selected from 2,5,8 tri(phenyl)-tri-v-triazolo(a,c,e)benzotriazole, 2,5,8-tri(nitrophenyl)-tri-v-triazolo(a,c,e)benzotriazole and 2,5,8-tri(dinitrophenyl)-tri-v triazolo(a,c,e)-benzene as tri-triazolobenzene derivative.
12. A composition as claimed in claim 1, 2 or 3 which contains at least one light-protective agent selected from digalloyl trioleate, phenyl salicylate, p-octylphenyl salicylate, tert.butylphenyl salicylate resorcinol monobenzoate and 2,4-di-tert.butylphenyl-3,5-di-tert.butyl-4 hydroxybenzoate.
13. A composition as claimed in claim 1, 2 or 3 which con-tains at least one light-protective agent selected from ethyl 1,1'-diphenylacryonitrilate, 2-ethylhexyl 1,1'-diphenyl-acrylo-nitrilate and methyl .alpha.-cyano-.beta.-methyl-4-methoxycinnamate.
14. A composition as claimed in claim 1, 2 or 3 which contains at least one light-protective agent selected from (2,2'-thiobis)4-tert.octylphenolate-n-butylamine-nickel(II), nickel-bisoctylphenyl sulfide, nickel-dibutyldithiocarbamate and 3,5-di-tert.butyl-4-hydroxybenzyl-phosphoric acid mono-ethylester 2:1 nickel chelate as metalorganic compound.
15. A composition as claimed in claim 1, 2 or 3 which contains 2-(2'-hydroxy-3'-tert.butyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3',5'-di-tert.butylphenyl)-5-chlorobenzotriazole as light-protective agents.
16. A composition as claimed in claim 1, 2 or 3 which contains 2,2',4,4'-tetrahydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid as light-protective agents.
17. A composition as claimed in claim 1, 2 or 3 which contains 2-ethylhexyl 1,1'-diphenylacrylonitrilate and 2-hydroxy-4-methoxybenzophenone as light-protective agents.
18. A composition as claimed in claim 1, 2 or 3 which contains 5-(3,3-dimethyl-2-norbornylidene)-3-pentene-2-one and 2-hydroxy-4-n-octyloxybenzophenone as light-protective agents.
19. A composition as claimed in claim 1, 2 or 3 which contains 2-hydroxy-4-n-octyloxybenzophenone and 2-(3'-tert.-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole as light-protective agents.
20. A composition as claimed in claim 1, 2 or 3 which contains 5-(3,3-dimethyl-2-norbornylidene)-3-pentene-2 one and digalloyl trioleate as light-protective agents.
21. A composition as claimed in claim 1, 2 or 3 which contains 2-ethylhexyl 1,1'-diphenylacrylonitrilate and 2-hydroxy-4-n-octyloxybenzophenone as light-protective agents.
22. A composition as claimed in claim 1, 2 or 3 which contains 2-hydroxy-4-n-octyloxybenzophenone, 2-(3'-tert.butyl-2'-hydroxy-5'-methylphenyl)-5 chlorobenzotriazole and 5-(3,3-dimethyl-2-norbornylidene)-3-pentene-2-one as light-protective agents.
23. A composition as claimed in claim 1, 2 or 3 which contains zinc oxide and 2-(2'-hydroxy-3'-tert.butyl-5'-methyl-phenyl)-5-chlorobenzotriazole as light-protective agents.
24. A composition as claimed in claim 1, 2 or 3 which contains 5-(3,3-dimethyl-2-norbornylidene)-3-pentene-2-one and zinc oxide as light-protective agents.
25. A composition as claimed in claim 1, 2 or 3 which contains 5-(3,3-dimethyl-2-norbornylidene)-3-pentene-2-one and nickel-bisoctylphenyl sulfide as light-protective agents.
26. A composition as claimed in claim 1, 2 or 3 which contains 2-(2'-hydroxy-3',5'-di-tert.butylphenyl)-5-chloro-benzotriazole and nickel-bisoctylphenyl sulfide as light-protective agents.
27. A composition as claimed in claim 1, 2 or 3 which contains 2-(2'-hydroxy-3',5'-di-tert.butylphenyl)-5-chlorobenzo-triazole and [2,2'-thiobis-(4-tert.octylphenolate)]-n-butylamine-nickel(II) as light-protective agents.
28. A composition as claimed in claim 1, 2 or 3 which con-tains 2-ethylhexyl 1,1'-diphenylacrylonitrilate and [2,2'-thiobis-(4-tert.octylphenolate)]-n-butylamine-nickel(II) as light-protective agent.
29. A process for the prophylaxis of apple peel spot wherein the apple is treated with a composition containing at least one light-protective agent together with a carrier, diluent or auxiliary agent useful in plant protecting composition.
30. A process for the prophylaxis of "Jonathan" peel spot, wherein the apple is treated with a composition containing at least one UV-absorber together with a carrier, diluent or auxiliary agent useful in plant protecting compositions.
31. A process as claimed in claim 29 wherein the composition further contains at least one other biologically active substance.
32. A process as claimed in claim 29, wherein the apple is treated with a composition containing at least one light-protective agent selected from benzophenone derivatives, benzo-triazole derivatives, dibenzotriazole derivatives, tris-triazolobenzene derivatives, aromatic ester derivatives substi-tuted acrylonitrile derivatives, metalorganic compounds and alicyclic dienone derivatives.
33. A process as claimed in claim 29, wherein the apple is treated with a composition containing at least one benzo-phenone derivative as light-protective agent.
34. A process as claimed in claim 29, wherein the apple is treated with a composition containing at least one benzo-triazole or dibenzotriazole derivative as light-protective agent.
35. A process as claimed in claim 29, wherein the apple is treated with a composition containing at least one tris-triazolobenzene derivative as light-protective agent.
36. A process as claimed in claim 29, wherein the apple is treated with a composition containing at least one aromatic ester derivative as light-protective agent,
37. A process as claimed in claim 29, wherein the apple is treated with a composition containing at least one substituted acrylonitrile derivative as light-protective agent.
38. A process as claimed in claim 29, wherein the apple is treated with a composition containing at least one alicyclic dienone derivative as light-protective agent.
39. A process as claimed in claim 29, wherein the apple is treated with a composition containing at least one metalor-ganic compound as light-protective agent.
40. A process as claimed in any of claims 29, 30 or 31 wherein the apple is treated more than once.
41. A process as claimed in any of claims 29, 30 or 31 wherein the apple is treated with a composition containing 5.0 to 0.1% by weight of a light-protective agent.
42. A process as claimed in any of claims 29, 30 or 31 wherein the apple is treated at most one month before harvesting.
43. A process as claimed in any of claims 29, 30 or 31 wherein the apple is treated by spraying.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HURI-595 | 1976-08-19 | ||
| HU76RI595A HU176150B (en) | 1976-08-19 | 1976-08-19 | New composition for the prevention of spots on apple peel |
| HURI000600 | 1976-10-28 | ||
| HURI-600 | 1976-10-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1102692A true CA1102692A (en) | 1981-06-09 |
Family
ID=26318561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA284,970A Expired CA1102692A (en) | 1976-08-19 | 1977-08-18 | Method and composition for the prophylaxis of apple peel spot |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5338648A (en) |
| AT (1) | AT348826B (en) |
| AU (1) | AU514160B2 (en) |
| BG (1) | BG28033A3 (en) |
| CA (1) | CA1102692A (en) |
| CH (1) | CH634463A5 (en) |
| CS (1) | CS207479B2 (en) |
| DD (1) | DD132563A5 (en) |
| DE (1) | DE2737502C2 (en) |
| FR (1) | FR2361818A1 (en) |
| GB (1) | GB1552277A (en) |
| GR (1) | GR63639B (en) |
| IL (1) | IL52707A (en) |
| IT (1) | IT1116792B (en) |
| NL (1) | NL7709195A (en) |
| PL (3) | PL119651B1 (en) |
| RO (1) | RO78663A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57207100A (en) * | 1981-06-16 | 1982-12-18 | Hamanaka Kk | Pasting handcraft method |
| JPS59164800U (en) * | 1983-04-18 | 1984-11-05 | 河口株式会社 | painting sheet |
| EA030181B1 (en) * | 2009-04-02 | 2018-07-31 | Басф Се | Method for reducing sunburn damage in plants |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5015695B1 (en) * | 1970-09-07 | 1975-06-06 |
-
1977
- 1977-08-11 IL IL5270777A patent/IL52707A/en unknown
- 1977-08-16 CH CH1003377A patent/CH634463A5/en not_active IP Right Cessation
- 1977-08-17 FR FR7725120A patent/FR2361818A1/en active Granted
- 1977-08-17 BG BG3718377A patent/BG28033A3/en unknown
- 1977-08-17 GR GR54179A patent/GR63639B/en unknown
- 1977-08-17 IT IT6887577A patent/IT1116792B/en active
- 1977-08-18 RO RO77100023A patent/RO78663A/en unknown
- 1977-08-18 DD DD20065077A patent/DD132563A5/en unknown
- 1977-08-18 CS CS544777A patent/CS207479B2/en unknown
- 1977-08-18 AU AU28027/77A patent/AU514160B2/en not_active Expired
- 1977-08-18 JP JP9831577A patent/JPS5338648A/en active Pending
- 1977-08-18 AT AT596977A patent/AT348826B/en not_active IP Right Cessation
- 1977-08-18 CA CA284,970A patent/CA1102692A/en not_active Expired
- 1977-08-18 GB GB3476677A patent/GB1552277A/en not_active Expired
- 1977-08-19 PL PL22867477A patent/PL119651B1/en unknown
- 1977-08-19 PL PL20036677A patent/PL118905B1/en unknown
- 1977-08-19 DE DE19772737502 patent/DE2737502C2/en not_active Expired
- 1977-08-19 PL PL22867177A patent/PL119519B1/en unknown
- 1977-08-19 NL NL7709195A patent/NL7709195A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| BG28033A3 (en) | 1980-02-25 |
| GB1552277A (en) | 1979-09-12 |
| JPS5338648A (en) | 1978-04-08 |
| CS207479B2 (en) | 1981-07-31 |
| RO78663A (en) | 1982-03-24 |
| DE2737502C2 (en) | 1984-05-30 |
| GR63639B (en) | 1979-11-27 |
| FR2361818B1 (en) | 1984-01-06 |
| FR2361818A1 (en) | 1978-03-17 |
| IL52707A (en) | 1982-03-31 |
| IT1116792B (en) | 1986-02-10 |
| PL200366A1 (en) | 1978-05-08 |
| PL118905B1 (en) | 1981-11-30 |
| PL119519B1 (en) | 1982-01-30 |
| NL7709195A (en) | 1978-02-21 |
| DE2737502A1 (en) | 1978-02-23 |
| CH634463A5 (en) | 1983-02-15 |
| AU514160B2 (en) | 1981-01-29 |
| AT348826B (en) | 1979-03-12 |
| AU2802777A (en) | 1979-05-10 |
| ATA596977A (en) | 1978-07-15 |
| DD132563A5 (en) | 1978-10-11 |
| PL119651B1 (en) | 1982-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Neant et al. | 6-Dimethylaminopurine blocks starfish oocyte maturation by inhibiting a relevant protein kinase activity | |
| Carter | Effects of cytochalasins on mammalian cells. | |
| Stefano et al. | Histofluorescent localization of serotonin and dopamine in the nervous system and gill of Mytilus edulis (Bivalvia) | |
| Kültz et al. | Mitochondria-rich (MR) cells and the activities of the Na+ K+-ATPase and carbonic anhydrase in the gill and opercular epithelium of Oreochromis mossambicus adapted to various salinities | |
| Tsvetkova et al. | Motility and fertilizing capacity of fresh and frozen‐thawed spermatozoa in sturgeons Acipenser Baeri and A. ruthenus | |
| Skoog et al. | Further experiments on the inhibition of the development of lateral buds by growth hormone | |
| AR012845A1 (en) | AMYLOID LIGATING COMPOUND, METHOD FOR SYNTHESIZING IT, CONTAINING PHARMACEUTICAL COMPOSITION AND ITS USE IN THE MANUFACTURE OF PHARMACEUTICAL COMPOSITIONS | |
| US20020068360A1 (en) | Cyclohexanediol cryoprotectant compounds | |
| Alavi et al. | Roles of osmolality, calcium—Potassium antagonist and calcium in activation and flagellar beating pattern of sturgeon sperm | |
| RU95108332A (en) | Indole derivatives and their tautomeric forms, mixtures of their isomers and pharmaceutical composition exhibiting antitumor activity or activity inhibiting protein tyrosine kinase and method of inhibition of protein tyrosine kinase-depending disease or struggle against aberrant cell growth in mammalian or human | |
| Guillard | A mutant of Chlamydomonas moewusii lacking contractile vacuoles | |
| CA2122002C (en) | Alteration of rate and character of hair growth | |
| CA1102692A (en) | Method and composition for the prophylaxis of apple peel spot | |
| US4839383A (en) | Compositions for combatting bark beetles | |
| ATE20736T1 (en) | CYCLOHEXANE 1-3 DIONE DERIVATIVES WITH HERBICIDAL ACTIVITY. | |
| Sagi et al. | Spermatogenesis and sperm storage in the testes of the behaviorally distinctive male morphotypes of Macrobrachium rosenbergii (Decapoda, Palaemonidae) | |
| US5063049A (en) | Disinfectant nail polish remover | |
| AR002853A1 (en) | SYNERGIC HERBICIDE COMPOSITION COMPRISING A CYCLOHEXANE DIONA COMPOUND AND A CHLOROACETHANILIDE COMPOUND AND A METHOD FOR CONTROLLING UNWANTED VEGETATION. | |
| Sanders | Toxicity of some insecticides to four species of malacostracan crustaceans | |
| DE69729104D1 (en) | PHARMACEUTICAL COMPOSITIONS CONTAINING TYRPHOSTINE | |
| SU1743330A3 (en) | Cockroach control method | |
| US4107302A (en) | Novel aqueous insecticidal concentrate composition | |
| DE59000195D1 (en) | PHARMACEUTICAL PREPARATION FOR TREATING LIVER DISEASES. | |
| US4238499A (en) | Method of killing ectoparasites with imidazoline and imidazolium toxicants | |
| Akita et al. | Ultrastructure of mouse incisor ameloblasts after vascular perfusion with colchicine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |