Note: Descriptions are shown in the official language in which they were submitted.
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
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
- 7
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~
269
~` 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~;~
18
.
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~
100
;~ 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
- 47 -
~'
