Note: Descriptions are shown in the official language in which they were submitted.
~ W0 95122897 2 ~ o 3 ~ 5 8 ~ . ,u
E'"ll ~IFIER COMPOSITIONS
This invention relates to emulsifier w" ,,uu ,iliu, l~, and in particular to , " ,~, which contain a
plurality of surfactants; to emulsifiable Wll~lltlc~d~, which are readily emulsifisble into water,
5 comprising the emulsifier composrtion, in particular w"~"~, dt~ with a high loading of a chemical
aûent with activity specific to the intended use of the w, ",~ ,ct~" to diluted fommulations
comprising the concentrate; and to processes for preparing or using the emulsmer , ' Ia,
the w, ,~, ,t,ct~,:,, and the diluted formulations comprising the oomposition.
10 Emuisifier , " ,~ with a plurality of surfactants are known in general in the cu,u~
industry; these may be used to fomm w, ~.UI ,~, cLels comprising a chemical agent with activity
specific to the intended use of the concentrate, and such cUIl~l~lldl~ are readily emulsifiable on
conversion to a diluted formulation. However, the efficacy of such emulsrfier , " ,~ as an
emulsifier and the extent to ~vhich the resultant w" ,uu~ ":, are readily emulsifiable into water to
15 a diluted fommulation is usually limited to a specific combination of a dispersed chemical a3ent and
readily emulsifiable surfactant w,, ,,uu, ,~"t~.
We have developed a class of vic-dicarboxylic acid r l~ OAy half ester derivatives as
described in published PCT Application No WO 94/û0508 A (PCT/GB 93/û1335). This invention
20 relates to applications of compounds of this general type of the fommula (I) or (Il) below
Y.A'.OC.(HR)C.C(HRI).CO.A(CmH2mO)n.R2 (1)
where
one of R and R~ is C~ to C22 alkenyl or alkyl and the other is hydro3en;
A is -O- or -NR~-; where R~ is hydrogen or C, to C~ alkyl, particulariy methyl or ethyl;
25 n is 2 to 100 (and as it is an average it may be non-integral);
m is 2 or 3 (and may vary along the U-2~UA/ . ", lcne chain);
R2 is hydrogen or C1 to C,~, particularly C, to C~ alkyl;
A' is -O-, -O or -NR4- where R~ is hydrogen or C, to C~ alkyl, particularly methyl or ethyl;
such that when A' is -0: Y is a cation, particularly H, and alkali metal cation especially a
30 sodium or potassium cation. or an ammonium ion (especially NH4~, an amine ammonium or
an " lùlc" ,i, le~ ammonium ion); and when A' is -O- or -NR4-: Y is a C1 to C~ alkyl group (R3)
or a group of the fommula (CmH2mO)n.R2 where m, n and R2 are i~ u~"~ , as defined
above;
or
35 Y.A1.0C.(HR)C.C(HR').CO.A(CnH2mO)n.CpH2p.A.CO.(HR')C.C(HR)CO.A'.Y (Il)
where: n, m and each R, R~, A, A' and Y are inde~u~:"~"~ly as defined above; and p is 2 or 3.
Wo95122897 2 1 838 ~8 2 - ~ lu
As descnbed in WO 94/00508 A, the free acid fonms of compounds of the fommulae (I) and (Il) in
are defined with Y as 8 Ht cation including both the ionised and non-ionised fomm of the free acids.
Compounds of the fomnulae (ll or (Il) are typically miAtures of isomers Wll~.lUll~.iillU to the two
senses of the snhydnde ring opening reaction typically used in their synthesis- The alk(enhl
5 chain seems to have a minor steric effect on the isomer ratio (typically about 60:40), the major
isomer arising from nucleophilic attack at the anhydride carbonyl group remote from the alk(en)yl
group. Thus in particular the compounds of the fommulae (I) and (Il) include those of the fonmulae
(la) and (lla):
R' - CH(CO.AY) - CHz CO.AZ (la)
10 in which
Z is a group of fonmula (CmH2mO)nR2 in which n, m and R2 are as defined for Fommula (I) aboYe
with n preferably being 3 to 50;
R2 j5 hydro~en or an alkyl group having 1 to 16 and preferably1 to 6 carbon atoms;
A and A' are each i"d~y~ -O-, -O- or -NH- groups,
5 when A or A' is -O- the respective Y is a cation for example H+ or an alkali metal ion,
when A or A' is -O- or -NH- the respective Y is a group R2 or (CmH2mO)nR2 where m and R2
are as dehned above and may be the same or different to the group Z,
R' is an alkyl or alkenyl group having 6 to 22 and preferably 13 to 20 carbon atoms,
or of fommula (lla):
20 R' - CH(COA'Y) - CH2-CO.A - D - A.OC - CH2 - CH(COA'Y) - R' (lla)
in which D is a group of fommula (CmH2mO)n CDH2p -
in which p is 2 or 3; and
R', A, A', m and n are as defined above for formula (la).
25 Various uses of compounds of this general type are described in WO 94/0û~û8 A, including as
emulsifying agents for acrylamide invert ,uu'~ , i " systems and as wool scouring agents. We
haveno~vfoundthatsuchcompoundsareusefulinemulsifierw,,,, ' ,:,withapluralityof
surfactants, which may be used to form w,~"~ . comprising a chemical agent with activity
specific to the intended use of the concentrate, and which w, ~ , are readily emulsifiable
30 into water. These emulsions are useful in general in the a_l uul I ' ' industry, such as in
fommulations which comprise a chemical agent which is known in the au, u-J I ' industry to
have an activity appropriate for use in weed, fungus or insect control.
According to a first aspect of the invention there is provided a composition which comprises
35 (a) at least one surfactant vic dicarboAylic acid l: 'y. "~ ùAy half ester denvative of the
formula (I) or (Il) as defined above; and
(b) at least one other surfactant.
~ W095122897 2 1 ~3858 ~ u
- 3 -
Particularly suitable emulsiher ~ of this first aspect are those uomprisin~q
(a) at least one compound of the fommula (I) or (Il) above, present as 5 to 90 wt.% of the total
composition, preferably as 10 to 75 wt.~6; and
(b) at least one other surfactant, present as 10 to 90 wt.% of the total, preferably as 10 to 70
5 wt.%.
The balanue of the uomposition may be a water miscible liquid and/or water imiscible, e.g. orsanic,
liquid. This may be desirable if the viscosity of the uomposition would othenwise be i"w".
hi5h. The uomponents and their proportions are preferably chosen such that where any
10 components are readily available only as aqueous solutions the composition provided by mixing
the composition uu~ uu, ~t:"~a iS stable, l l ' la~al Idil l~ the water which is thereby introduued.
The uomposition often employs a half-ester derivative containing anionic groups and/or in
particular sroups ionisable to anion. Preferred such ester derivatives are generally as set out in
15 WO 94/00508 A, but preferred surfactants of this type include mono- and di-ester derivatives
within fommula (I) or (Il) respectively in which the alk(en)yl substituent on the succinic moiety
preferably has 8 to 20 carbon atoms. This is particularly the case in the dUI U~l I ' ' industry
when used to form an emulsrFiable concentrate comprising a chemical agent with activity specific
to the intended use of the concentrate. Particuiar ester derivatives of this type include those in
20 which the alk(en)yl substituent has 10 to 17, preferably 12 to 14 carbon atoms, and especially
where it is an alkenyl ~qroup. Prefenred such vic-dicarboxylic acid uu~j 'h~"aoA~ half ester
derivatives also include those in which Z (in fommula (la)) is an alkylene oxide (block) (co-)polymer
of fommula (CmH2mO)nR2 as def ned in which n is preferably 7 to 13 and m is 2 andlor 3. As
desuibed in WO 94/00508 A, the alk(en)yl groups in the surfactants of the fonmula (I) or (Il) used
25 in this invention are desirably linear alk(en)yl groups.
The other surfactant(s) may be any which on usin~ the emulsifier composition in the fommulation of
a concentrate comprising a chemical agent with activity specr~ic to the intended use of the
uoncentrate, will sive a concentrate which:
30 (a) is stable and I ,u" luue"eu.ls for at least 24 hr. after makin~ up; and
(b) remains homooenous on dilution with water to a diluted fommulation.
The other surfactants which are suitable for such stability in use and storage of the concentrate
may be anionic, cationic, amphoteric or non-ionic surfactants, or mixtures thereof. Suitable
35 anionic surfactants include members of the alkarene sulphonate salt group, such as alkyl benzene
sulphonate salts having 6 to 16 carbon atoms in its straisht chain or branched chain alkyl group,
e.s. wherein the alkyl is lauryl (dodecyl), or mixtures thereof; members of the poly(arylaryl-
WO 95/22897 . ~,1,. ' Iu
2 1 ~3858 ~ --
- 4 -
alkoxylate) phosphate or sulphate salt group; members of the alkaryl phosphate or sulphate salt
group; members of the straight chain or branched alkyl- and alkoxylated alkyl phosphate or
sulphate salt group; and membens of the fatty aàd salt group, having 8 to 24, preferably 12 to 18,
carbon atoms, e g. Iaurate, I lelJ~elde~l lud~e, l~e,u~ud~l enuaLe, stearate and oleate; and members
5 of the ~roup of salts of alkoxylated w, bUA~ !_W alkaryl and fatty alaohols, the latter including e.g.
.Yk,. ~e OXide)C12 b ~5 aIaOhOI IrIe~ UA~ Examples of suitable salts include those
with an alkali metal cation e.g. sodium or potassium; an alkaline earth metal, e.L3. calcium; and
ammonium, aliphatic ammonium " ,u'.~. "- "u"iu" . cation, wherein the aliphatic or alkanol
moieties are e.g. straight chain or branched alkyl having 1 to 4 carbon atoms; and mixtures
1 û thereof.
Inparticularwhentheaompositionisusedintheay,u~l,t,,,,iwlindustrytofommanemulsifiable
conoentrate comprising an ~u, u~ el "iwl agent with activity specLfic to the intended use of the
concentrate, prefen ed component (b) anionic surfactants include ~ el l~el ,t, sulphonate salts
15 having 6 to 16 carbon atoms in their strai~ht chain or branched alkyl group, e.g. wherein the alkyl
is lauryl. Preferred salts include the calcium salt.
Suitable cationic surfactants include alkoxylated fatty amine salts having 8 to 24, preferably
containing more than 12 carbon atoms, and in partiaular 12 to 18 carbon atoms, the latter
2û including e.g. poly(ethylene oxide) C,zb,5 amine salts, e.~. chloride salts.
Non-ionic surfactants are particularly useful in Wl l~ lLl d~ which are readily emulsihable in
particularinau,u-,l,t,,,,i-,dlw,,~e,,~,dL~. Theseincludenon-ionicsurfactantsusedinthe
~u~ uul ,~",i~al industry to fomm emulsifiables, in particular those of the formulae:
R2l.0(X)RZ' andlor R2'- N (-XH)2
in vJhich
R2' is an alkyl group or alkenyl group which suitably contains up to 24, preferably 6 to 21, and
especially 9 to 18 carbon atoms, an alkyl phenol group having 6 to 12 carbon atoms in its
alkyl group, a sorbitan group or a group of formula R"C0 in which R2' is an alkyl group
3û haviny 11 to 22 carbon atoms;
Rn is hydnogen or an alkyl group, a w, UUA; "<~,1 group, e.g. Udl L , _"<~,l having 2 to 4 carbon
atoms, or a fatty acid residue having 10 to 22 carbon atoms;
X is a r 1~ !k, ' ,~ oxide group containin3 an average of 2 to 40, preferably from 2 to 13, and
especially from 2 to 10 alkylene oxide groups or mixed alkylene oxide groups; and
35 R2' is an alkyl or alkenyl group having 10 to 22 carbon atoms.
~ W095/22897 2 1 8 3 ~ ~ 8 ~ u
-- 5 -
r Aamples of suitabie ~roups R2' include e.s. sorbitan and :auryl, heptadecyl, I~ J~ad~:l.,~l,
h-~ , stearyl and oleyl. -xamples of suitable sroups R22 include e.3. carboxy-rnethyl,
~thyl or -propyl, or a salt thereof; and laurate, I ,~:,u~c,d~ c"u~ ,uic.~ u.. ~.,
luc~el, stearate or oleate. i xamples of suitable X include, '~ ~l "<y!~.. ,e or5 mixed alkylene oxide) groups, wherein the alkylene ~roups each have 2 to 8, preferably 2 to 4,
e.g. 2 or 3 carbon atoms, and, when R2' is sorbitan, and R22 is fatty acid residue havin3 1û to 22
carbon atoms, a direct bond.
r~xamples of suitable non-ionic surfactants thus include i~û'y~ ,1) fatty acids and alcohols
10 having 8 to 24, preferably 12 to 18 carbon atoms in their fatty acid or alcohol Sroups;
') alkaryl alcohols havins 8 to 24, preferably 12 to 18 carbon atoms;
') ~ " , !L'~,~) sorbitan and sorbitol esters; poly(; " , '_:~.1) tri~lycerides, including e.g.
'~ I) vegetable oils, such as poly(ethoxylated) linseed oil, mustard oil, neem oil, niger
seed oil, oiticica oil, palm oil, palm kernel oil, peanut oil, perilla oil, poppy seed oil, safllower oil,
15 sesame oil, or (especially) soybean oil; poly(alkoxylated) allyl alcohols; poly(alkoxylated)
poly(arylaryl alcohols); and poly(~ ,"~, oxides) including (block) (co-)polymers; in particular
those wherein the alkylene ~roups each have 2 to 4 carbon atoms; and sorbitan esters with up to
3û carbon atoms, such as sorbitan monooleate.
2û Within prefenred emulsifier w, I, ~s of the first aspect of the present invention, especially
when used for fonmulations for application in the au,u,.i ' industry, the component (b) (at
least one other surfactant) is
at least one non-ionic surfactant, and optionally
ii at least one anionic surfactant.
Prefenred component (b) non-ionic surfactants then include those of the formula: R210(X)R22 and/or R2' - N (-XH)2
as defined above which are indicated as prefenred non-ionic surfactants l ~ ru~ts.
3û Prefen-ed component (b) anionic surfactants then include ~ sulphonate salts having 6
to 16 carbon atoms in their straight chain or branched alkyl oroup, e.g. wherein the alkyl is lauryl.
Preferred salts include the calcium salt.
Preferred emulsiher wlll,uuai~iul ,:, of this first aspect are those comprisin~
35 a at least one vic-dicarboxylic acid I ') . 'ky~,, leOAy half ester derivative, present as S to 9û
wt.% of the total concentrate, preferably as 1û to 75 wt.%; and
WO 95/22897 2 1 8 3 8 5 8 ~ u
-- 6 -
b i at least one non-ionic surfadant, present as 10 to 90 v~t.% of the total, preferably as
10 to 50 wt.%, e.g. 10 to 40 wt.%, in particular 10 to 35 wt.%; and
ii optionally at least one anionic surfactant present as 0 to 60 wt.% of the total
composition, preferably as 0 to 40 wt.%, e.g. 15 to 40 wt.%, in particular as 25 to 40
wt % of the total.
One class of such emulsifier , ' ,~ is of those compnsing at least one anionic surfactant as
15 to 40 wt.%, in particular as 25 to 40 wt.% of the composition. Another class of composition is of
those comprisin3 no anionic surfactant. Examples of suitable water miscible liquids which may
10 fomm the balance of the composition and which may be desirable if the viscosity of the composition
would otherwise be i,,.,u,,~. Iiel1, high include alcohols, including glycols, e.g. with straight chain
or branched alkyl having 1 to 8 carbon atom, such as isobutanol and propylene glycol. Such liquid
may often contain water, which is thereby introduced into the composition, and may be present as
up to 3 wt.% of the total.
Examples of suitabie water imiscible liquids which may form part of the balance of the composition
and which may be desirable if the viscosity of the composition would other~vise be i,~cul, . _. Iiel 1;'~'
high include 1 ,~l u~.al L~ul 1~, preferably those having 5 to 18 carbon atoms, including aromatic
l.,llu-,a,L,u,,:,,straightchainorbranchedalcohols;optionallyl,~d,vut:,,dtedvegetableoils,such
20 as an optionally ~.ydl uuel laLed cotton seed oil, linseed oil, mustard oil, neem oil, niger seed oil,
oiticica oil, olive oil, palm oil, palm kernel oil, peanut oil, perilla oil, poppy seed oil, rape seed oil,
saf~lower oil, sesama oil, or soybean oil; esters (especially a C1-6 ester) of a C8-Z fa~ty acid,
especially a C12-18 fatty acid, e.g. members of the group comprising methyl laurate,
uLadaCal lua~e, l~euLa~e~,el lUa~ . IUC~, stearate or oleate, in particular methyl
25 laurate and oleate; N-l1 le~l 1) 'IJ, .1 l " ' le, and iSuual a~ril la, or a mixture thereof. Preferred such
liquidmaterialswhichmaybeusedincludexylene,anymixtureofaromaticll,~, u~alLu~1:,, and
N~ U1~ a~
According to a second aspect of the invention there is provided an emulsinable concentrate
30 compnsins the emulsifier composition of the first sspect; snd
(c) st least one chemical agent with activity specific to the intended use of the concentrate.
Such chemical agent specific to the intended use of the concentrate may be for example an
a~lul,l I ' or a metal corrosion inhibitor.
35Ifan a~lu~91elllil.àlis presentitistypicallyoneormore~ la~2;a~ forexsmplegrowth
re~ulators or herbicides, snd/or pesticides, for exsmple insecticides, fungicides or scaricides.
Such Gul luel ILI a~eS may comprise a second chemical sgent vihich will give 8 concentrate in which
21 83858
wo ssn2ss7 ~ . /U
- 7 -
the activity of the first chemiQI agent is made more specific to or selective in the intended use of
the concentrate or w" ea,uul Idil ~y dilute formulation. Such W~WI Itl ate ~ typiQlly include e.g.
w, ,u:, Itl dtaa in which the first chemical a~ent is an ayl u~,l ' which is one or more
~JI 1, . , for example ~rowth regulators or herbicides, and/or pesticides, for example
5 insecticides, funsicides or aQricides, and the second is a ~JI i,: ' ~ inhibitor to regulate any
, for example growth regulation or herbicidal actiYity of the conoentrate or
w~ u~ ,.li, Iy dilute fonmulation, or e.3. Safener inhibitor to make it more selective, e.g. as
between graminious and broad leaved species. Such a second chemiQI asent may be present as
up to 15 wt.% of the total conoentrate.
Preferred w, I~.el ~ aiaa are those with a high loading of the chemiQI agent with activity specific
and appnopriate for the intended use of the composition. These exhibit dispersion even of specihc
chemical agents, such as ~icetochlor and Alachlor herbicides but also pesticides, such as
insecticides, funsicides or acaricides, which are known in the ~u' u..~ ,cll industry as not usually
15 readily emulsified.
Prefenred emulsifiable w, luel Itl d~e:~ of this hrst aspect are those comprising
(a) at least one vic-diQrboxylic acid ~ ') 'h, ~ UA; half ester derivative, present as 0.1 to 15
wt.% of the total conoentrate, preferably as 0.15 to 10 wt.%;
20 (b) at least one other surfactant, present as 1 to 25 wt.% of the total; and
(c) at least one chemical agent with activity specific to the intended use of the concentrate,
present as 2.5 to 95 wt.% of the total, preferably as 10 to 50 wt.%.
The greater part of the balance of the concentnate may be a water miscible liquid and/or water
25 insoluble organic solvent, to aid the dissolution of the chemiQI agent with activity specific to the
intended use of the concentrate om,ul, a:,~uul Idil 1 ~ dilute fonmulation. It may also be desirable U the
viscosity of the conoentrate would otherwise be i"..u" :,,, liel IIIy high. The conoentrate, in particular
when used in fommulations for appliQtion in the ayl uul, ' industry, may comprise one or more
such liquid and/or solvent w,,,~,u, lel ,t~ as 0 to 97, and in partlcular as 5 to 90 wt.% of the total
30 concentrate. In some intended uses of the w, ,~"~, clIe~, e.g. in methods of applyin3 tu, . ~' " ;D
of some srowth regulators, herbicides, insecticides, tungicides or aQricides, it is prefenred that the
concentrate has a significant water content, e.g. over 25 wt.% of the total. Such w, I~,el ,~ dL~a are
in fact w, ,vc, ,~, d~e l emulsions which are further emulsifiable on being diluted with water to give
fommulations for applyiny e.y over crops. The w~ u~ lel ,~, and their proportions are preferably
35 chosen such that the concentrate provided by mixiny the concentrate components is stable,
r ' ::: lalal Idil Iy the water which is thereby introduced. When the concentnate is a w~ ",~:"I~ a id.l
emulsion intended e.g. for use in the aul u~,l I ' ' industry to give fommulations for applying over
WO 95/22897 2 1 8 3 8 5 8 r ~ u ~
- 8 -
crops, certain emulsrFlable "u, ,u~ LI dt~ 2re those in which the components and their proportions
are:
(a) at lesst one vic-dicarboxylic acid I ') ", ~,"euA~ half ester derivative, present as û.1 to 15
wt.% of the total concentrate, preferably as û.2 to 10 wt.%;
5 (b) at least one non-ionic surfactant component as 1 to 25 wt.% of the total emulsiflable
concentrate; and
(c) no anionic surfactant.
Each of the present .,u, ,~"~, dttà
1û a exhibits dispersion even of specific chemical a3ents, such as Acetochlor and Alachlor
herbicides but also pesticides, such as insecticides, fungiades or acariddes, which are
knowninthe~u,u.,l,u,,,i,,dlindustryasnotusuallyreadilyemulsifiedbyknownsurfactants,
b remains a homosenous concentrate on dilution with water to make the concentrate into a
diluted fommulation of the present invention for application of the component (c) of the
15 concentrate, without the need for the addition of any further materials to disperse the phase
and prevent settling of the phase from the diluted ~,u, ,-,~" ,t~ d~e,
c exhibit excellent wetting properties in relation to the dispersed chemical agent in the
concentrate herein described, and in particular in relation to treated substrates.
2û Preferred , " la of the present invention, especially when used for cu, ",~"t, elLda and
fommulations Of clUI ud " ~ ,dla, enable a hi~3h loadin3 even of the agents referred to in (a) above,
for example herbicides such as Acetochlor and Alachlor Suitable and preferred vic-dicarboxylic
acid p~l~ lky,c.l~uA~ half~ster derivatives and other surfactants in the concentrate are generally
those so described l~ lL,~u, ~: with regard to the emulsiher -,u" ,uu:.;Liu"a of the first aspect of
25 the invention.
Examples of suitable water miscible liquids include alcohols, includin~ ûlycols, e e.g. with straight
dhain or branched alkyl having 1 to 8 carbon atoms. Preferred examples include isobutanol and
propylene glycol. Such liquid may often contain water.
3û
EAamples of suitable water insoluble organic solvents which may fomm part of the balance of the
concentrate include l ', ~ UUdl ùu, la, preferably those having 5 to 18 carbon atoms, includin6
aromatic h~ ~, u~, L,u, la, straight chain or brandhed alcohols; optionally ~ u~ eJ vegetable
oils, such as an optionally h~ ~l u~ dL~ld cotton seed oil, linseed oil, mustard oil, neem oil, niger
35 seed oil, oiticica oil, olive oil, palm oil, palm kemel oil, peanut oil, perilla oil, poppy seed oil, rape
seed oil, safflower oil, sesame oil, or soybean oil; esters (especially a Cl ,0, ester) of a C~,022 fatty
acid,especiallyaC,2,0,~fattyacid,e.g.membersofthegroupcomprisingmethyllaurate,
~W09~122897 21 83=858 ~ u
g
-~, I,e~"a.le.,enu~t~ ud~e, stearateoroieate, inparticularmethyl
laurate and oleate; N-n ,e~ "~ , and i;,u,uc", ~~ ,a, or a mixture thereof. Prefenred such
solventmaterialswhichmaybeusedincludexylene,anymixtureofaromaticl,~lu~,L,u"~,and
An anti-foam agent may be present. A sufficient quantity to provide an anti-foamin3 eflect for the
intended use of the concentrate without separatins out is desinable. Nommally û.05 to 10% and
prefenably 0.2 to 6% by weight of the total is suitable. Any compounds may be used which are
w,,. ., 'iy useful as anti-foam agents in aqueous fonmulations with a hi3h dispersed phase
10 content. The antifoamin3 a3ent(s) is/are preferably one or more u.,'~ ' ,es, especially of the
type havin3 hydrophilic 3roups. It is preferably of fommula
R~3 SiO [SiO R' R~lnSi R~3
in which
the 3roups R~ are individually alkyl groups, preferably havin3 1 to 3 carbons atoms and are
15 preferably methyl 3roups, one or more of the qroups R may be residues of polyalkylene
31ycols and the others are as defined for R~.
The groups R~ preferably have a molecular wei~ht in the range 1000 tû 20000 and especially 5000
to 15000. Examples of suitable, '~ ' ,e antifoams are disclosed in British Patents 1533610
and 1 554736.
Other possible additives in the emulsifiable w, ,w, ", ~te:~ to which this invention relates include
non-surfactant materials which are ,,u, . .~. ,Liu, ,~''y useful in surfactant fommulations as viscosity
modifiers, stabilisers, and anti-microbials. One class of known viscosity modifier materials of this
type includes one or more uullllllel-,i~:'y available water soluble or miscible materials such as
25 sums, e.3. xanthan gums, and cellulosics, e.g. carboxy-methyl, ethyl or propylcellulose. These are
oftenpresent,whenusede.g. in~,,u-,l,c,,,iudlfommulationsinparticularas001 to1 v~t.%ofthe
total w~ I~,el ,L,
The present emulsifier concentnate may have a pH value within a range of for example 5 (acid) to
30 9 (alkaline), for example 6 to 8.
The emulsi~lable ~, ,~,c, ,~, clLea to which this invention relates may be produced by Wl l .'~,. l'' ~CI
mixin3ofthew,,,,uu,,_.,tainanyorderusedcu,,~.,~
.
35 In a third aspect the present invention thus provides a process of makin3 the concentrate by
mixin3 the 1UII IUUI lel ILa together. This may be effected for example by addin~ the components (a),
wo g5/22897 2 1 8 3 8 ~ 8
(b) and (c), and any other components e.g. solvents and/or any other additives, and stirrin6 until
the product is llul--vuelleOUs.
For emulsifiable w, I~,el ,t, aLas to which this invention relates which are w, 11~1 ,L, d~a~ emulsions,
5 mixing the components in a speciflc order may be necessary. Such emuisifiable ~,u, I~,el ,L, dlea may
have to be produced by separate cu~ . " lal mixins of
a the components of the vehicle liquid, and
b the components (a), (b) and (c) and any other components, respectively, to sive two
separate liquid phases, with stirrins until each product is homoseneous.
10 The concentrate is made by careful dispersion of the phase containin3 the components (a), (b)
and (c) in to the other phase. It is may be desirable that this is effected for example by addin~ the
phases at moderately elevated temperatures with high shear mixing to deal with the il ,w, 1. ~, liel ,t'~
hish viscosity of the concentrate which is thereby introduced. The product w"~ "LI aled emulsion
is subsequently left to cool to ambient temperature.
In most applications, the surfactant l,u, 1~1~1~ cl1ea of the second aspect present of the invention will
suitably be supplied in a their (more ,u, I~l ~11 dL~ ) fomm and converted to a more dilute fonm at the
pointofuseinsuchapplications. Goodstabilityinstora3eofthemore.,v,,~,e,,L.dLedfommas
supplied before beins converted to a more dilute fomm at the point of use is still required. In a
2û fourth aspect the present invention provides a formulation which is a mixture of the components
(a), (b) and (c) of the concentrate accordins to the second aspect of the present invention with 1 û
to 1 û,ûOO times the total weisht of the , . Iel l~a (a), (b) and (c) of water, e.g. with 30 to 1,000
times the total weight of the components. This formulation accordin~ to the fourth aspect of the
invention may of course comprise othem,ullluull~llLa and additives. Suitable and preferred such
25componentsandadditivesareassodescribedl~elc:i,l'vetu,ewithre3ardtothe, 1 '' la,e.g.
solvents and anti-foam sgents, which may be desi~nated as components (d).
The fommulation may be made up in various ways, by for example
(i) mixing the components (a), (b) and (c) and (d) to form the concentrate and then diluting the
30 concentrate by mixing it with water to fomm the formulation; or
(ii) mixing components (a), (b) and (c) to fomm a concentrate and dilutins the concentrate with
water to fonm a fommulation, as appropriate mixins the components (d) and dilutin3 the
mixture of these components with water to form a second mixture, and mixin3 the nrSt
fommulation and the seoond mixture to fomm the desired fommulation according to a fourth
35 aspect of the present invention.
Such a process for preparin5 the formulation accordins to the fourth aspect of the present
invention fomms a fiRh aspect of the invention.
~ WO 95/22897 2 1 ~ 8 r ~
In all such processes for preparing the fommulation accordin3 to the invention, the ratio of the
weight of water used to the total wei3ht of the w" ,uu~,~"~ . (a), (b) and (c) of the fommulations of
the second aspect will of xurse be adjusted as appropriate to give a final fommulation of the
components (a), (b) snd (c) with in the definition above.
J 5
In a sixth aspect the present invention also pnovides a method of applying the fonmulation
according to the fourth aspect of ths present invention to a substrate
,1~ of this method include
a a method of treating vegetation by applying to plants and/or soil such a formulation
1 û according to the invention which fommulation compnses a speciflc chemical agent which is
an aul ul,l lt:llli~,dl
b a method of working metal which compnses applying a fommulation according to the
invention to the metai which fonmulation optionally comprises a specific chemical a3ent
which is a metal corrosion inhibitor
15 In ~ ' " ,L a the dUI Ul.l I ' ' may be one or more ul l,h , for example growth
regulators and/or herbicides, and/or pestiades, for example insecticides, fungicides or acaricides
This ~:",~uù" "~ of the method of applyin3 the fommulation accordin3 to the fourth aspect of the
present invention thus includes in tunn
(i) a method of killing or inhibiting ve3etation by applying the fommulation which comprises a
2û specific chemical agent which is one or more ,ul ,, ~ , for example gnowth regulators
and/or herbicides, and
(ii) a method of killing or inhibiting plant pests by applying the formulation which comprises a
specific chemical a~ent which is one or more pesticides, for exampie insecticides,
fungicides or acaricides.
251n~,,,L,ud,,,,~,,l(i),theeffectoftheauru~ ,,,i~l,whetheroneormore,ul,y~ut..,~;Jcs,forexample
growth re~ulators and/or herbicides, and/or pesticides, for example insedicides, fungicides or
acaricides, may be potentiated by the surfactants. In: ' ' ,L (ii) the workin~ of the metal may
include for example cutting or abrasion
3û Within w"~"~,dt~ and fonmulations of the present invention which comprise as component (c)
an aul u-.l, 31, this is typically one or more ,ul If ~U..~'i . _s" for example growth regulators andlor
herbicides, or pesticides, for example insecticides, fungicides or acancides i~xamples of such
~u~ r,~ " ~ appropriate for the intended use of the composition include an ~u~ uul, ' which
is one or more pl ., !uc~ D, for example herbicides such as Acetochlor, Alachlor and Trifluralin,
35 and also pesticides, for example insecticides such Propar~ite and Fenitrothion, and fungicides
such as r, uuiw, l~ult
WO9~/22897 21 83858 r~ u
- 12 -
Within cu, ~,O~ ~8 d~oS and fommulations of thô presOnt invention which comprisO as component (c)
an clu~ u~,l lolll;~,dl, somO comprisO a potentiator or inhibitor of thô working of the au" ' ' U
an ~Iu.,l loll ,;~l which is one or more ~ul Iyt ' , for OAample growth resulators or herbicidOs,
is present, and an inhibitor dU~ u~.h ' is also present, it may typically be a ~UI ~ U~UA;~ Y
S inhibitor~ Examples of suitable such materials include Safener.
Within w, ,~, IL dtoa and fonmulations of the present invention, some comprise a conrosion inhibitor
as componOnt (c). These may be used in a method of worhng metal which comprises applyin3 a
fommulation according to the invention to the metal which compnsOs such a chemical agent. One
1 û class of known corrosion inhibitors, suitable for practically all the relevant substrate matOnals
which may be trOated, includes straight chain or branched alkanO carboAylic acids and water
soluble salts thereof e.g. with an alkali metdl cation e.3. sodium or potassium, or an
" ,.,ld,l,-"u,liumcation. Materialsofthistypeincludeinparticularwatersoluble
ul~ "" ,u/ ~;um salts of straight chain or branched alkanO carboxylic acids which acicts
15 comprise 8 to 11 carbon atoms.
2û
3û
~ wogs/22897 21 83858 1~11. ,~,
- 13 -
The present inYention is illustrated by the following Examples. All parts and pe,~"ta~ . are by
weight unless otherwise stated. Example references suffixed by 'c' are for comparison purposes.
E~AMPLE 1
J 5 Preparation of Emulsifier Cl Ia
The emulsifier la shown in Table 1 were made by addino the components in the stated
amounts in a simple mixin~ process with stimng as appropriate. The components in Table 1 are
as follows:
H1 Half Ester Derivative of the fommula:
Y.O2C.(HR)C.C(HR').CO,(CmH2mO)~.R2
where Y is H one of R and R1 is C1~H,5 and the other is hydro3en m is 2 n is about 23
alJùl Idil l~ to PEG 1000) and R2 is H.
A Anionic Surfactant calciumd~ "~t"esulphonate
N Non-lonic Surfactant Atlas G-5000 surfactant (lCl)
15 W Water Miâcibie Liquid isobutanol
S Solvent Solvesso 100, aromatic l ,~ dl u~, Lul~ solvent
mixture (Exxon Chemicals)
Table 1
Comp % w/w of Components
No
H1 A ~ S W
~ ~,o O 30.8 ~.o 13.0 13.2
'' 0.0 ''~.0 ~, .0 1 ~.0 1 ~-,0
3 50 0,3.G i~.0 1~.0 1~.4
, ~o o .9 ~ o ~.O fi.c.
. 0.0 3-u ~0 Y.0 ~
ii 0.0 .,6.~ -~1.0 q.O ' .fi
c - 3O.~ ~3 0 3.0 .,.
" c - ' R.u ~.,.n .n ~ -.o
3û c - 3. , I " ~,
~ C - 1!1, .0 ,U ' ~
. ' C - ~ q.U ~l Q fi
c ~,~ ~q,~ ,o .
wo g5n28~7 2 1 83 8 C; ~ u
- 14 --
F~AMPLE 2
Preparation of Emulsifiable Concentrate and Diluted Fommulation; Testing of Fommulation
The above emulsifier ~ E1 to 6 and E21 c to E61 c were fommulated into w" aauul l-lil "~ -
wl)Cal Itl ~Las shown in Tables 2, 4, 6 and 8 by addins the components in the stated amounts in a
5 simple mixin3 process with stirring as appropriate.
The above w, l~al l~la~a:~ were fommulated into w" a~ ul ~di"-J diluted fommulations by adding the
w, ,~. ,tl u~a~ to water with the following parameters described above the relevant Table in each
case as appropriate: to the given % wt.lvol. dilution rate (suitable for the given desired use of the
10 given (diluted) concentrate), at the given temperature at the given WHO standard hardnesses of
342 and 50û ppm, and with the formulations being left to stand for the ~iven length of time.
The efflcacy of each emulsifier composition used in the w, Ical ,~, d~à~ shown in Tables 2, 4, 6 and
8intheformulations,.ul,a.,uu"-li"~u,tothe.ù"~ ,dlc,~sisshovJninTables3,5,7and9
15 respectively, in which the numbering of each formulation w, ~ ul l-l~ respectively to the
numbering of each concentrate, and the ~Igures are the volume of the disperse phase of the
concentrate (which contains the components (a), ~b) and (c)) which separates from the other
phas~.
Table 2
2ûConcentrate C1 ¦ C11
Component wt./vol. of Components
Alachlor ~herbicide) 480 9 480 9
E 40g
E - 40~
xyene to 11 to 11
Table 3
2 % wt./vol. dilution at25C - Standard Water Hardness 342 and 500 ppm
Formulation F1 ¦ F11
Haroness cream separation ~ml)
30 342 ppm NS ¦ 3.5 C
500 ppm NS ¦ 3.5 C
NS = no separation of the emulsion
~ WO 95/22897 2 1 8 3 8 ~ 8
- 15 -
Table 4
Concentrate C2 ¦ ,3 ¦ C2c ¦ C3c
Component w.ho . of Cnmponen s
Acetochlor(herbicide) 94%active 520g 5~06 920g 530g
5 - fener (,ul ,, ' ' ~; inhibitor) - ~0g - 70
803
-80g
' 1c - - 80g
11 c ' ~ ~ 809
~olvesso 100 - 320g - 320g
Table 5
5 % wUYol dilution 30C - Standard Water Hardness 342 ppm
Fonmulation F2 ¦ F3 ¦ F2c ¦ F3c
Standing Time (hr) cream sepsration (m )
15 0.5 TC ¦ TC ¦ 0.25C 6C
1.0 0.25C ¦ 0.25C ¦ 0.5C 6C
TC = trace (~ 0.05%) separation of the emulsion
Table 6
Concentrate C4 ¦ C4c
.omponent Compnnents
enitrothion (insecticide) 520g 520g
3 1 009
~31 c - 1 00g
25 .olvesso 150 to 11 to 11
Solvesso 150 = aromatic hydrocarbon solvent mixture, (E)o~on Chemicals)
Table 7
5 % wt.lvol. dilution 30C Standard Water Hardness 20 and 500 ppm
ormulation F4 ¦ F4c
ardness (ppm) 20 ¦ 500 ¦ 20 ¦ 500
. '~tanding Time (hr) -eparat on (ml)
0.5 1~ ~ ~ 9 OC 9 OC
2 1~ . 9C+TOC 5Cf30C
24 1~ 1 C+7O 8C
35 NS = no separation of the emulsion
OC = oily cream separation of the emulsion
_ _ , _ . _ _ . _ _ _ _ . ... ... ....... .....
WO 95122897 1 ~,1,. lu
2~83~58
-- 16 -
C = cream separation of the emulsion
TOC = trace (~ 0.05%) oily cream separation of the emulsion
O = oil separation of the emulsion
5 I ble8
Concentrate C5 ¦ C6 C7 ¦ C51c ¦ C61c ¦ C71c
~;omponent ~. of Com onents ( )
'ropargite (insecticide) 635 635 635 635 635 635
- -80
c - - - 80
! C - - - - 80
fi C - - - - - 80
. ylene 322 322 322 322 322 322
Table 9
1 % wt./vol. dilution 30~C Standard Water Hardness 342 ppm
Fommulation F5 ¦ F6 ¦ F7 ¦ F51c ¦ F61c ¦ F71c
Standing Time (hr) separation (ml)
200.5NS NS NS 0.5C + 0.5 C 1 C +
TO + TO TO
NSNS NS 0.5 C TC + TC +
0.50 1 0 1.20
2NSNS NS 0.5C TC+ TC+
0.50 l 0 1 0
4NSNS NS O.5C+ TC + TC +
0.50 10 10
24NS NS NS TC NS 0.5C +
0.70
NS = no separation of the emu~sion
TC = trace (< 0.05%) oily cream separation of the emulsion
30 C = cream sepanation of the emulsion
TO = trace (< 0.05%) oil separation of the emulsion
O = oil separation of the emulsion
~ WO 95/22897 2 1 ~ 3 ~ :~ 8
- 17 -
EXAMPl F 3
Prepatation of Emulsifer C , ' ,a
The emulsifier ,~ a shown in Table 10 were made by adding the components in the
stated amounts in a simple mixing process with stirtins as appropnate. The half ester derivative
5 component H2 in Table 10 is of the fommula:
Y.02C.(HR)C.C(HR').CO2(CmH2mO),.R2
where Y is H, one of R and R1 is C"H27 and the other is hydrogen, m is 2, n is about 14
(wllc7~,uulldill~to PEG6ûO)and R2 is H.
1 û Table 10
~ ~ , I 7 ¦ E8 ¦ E9
Component c; w/w of Components
~2 ~5 1 50 1 -
Atlas G-5ûO0 5 ¦ 5û ¦ 1ûO
FXAMPLE 4
Preparation of Emulsifable Concentrate (Concentrated Emulsion) and Diluted Formulation;
Testing of Fonmulation
Theaboveemulsiflerw,,,uu:.iLiu,,aE7toE9wereformulatedintow,,a:,,uu,,~i,,ucu,l,,e,,lld~a
20 shown in Table 11 by adding the components in the stated amounts In the following mixing
process
The Acetochlor active material, the Safener, the poly(ethoxylated) soybean oil and the
respective emulsifier composition E7, E8 or E9 components on the one hand, and the
propylene glycol and the water on the other were mixed separately at 50C with stirring until
25 each product was l~ul~luue~ UUS, to give two separate liquid phases, ('phase B' and 'phase
A' tespectively).
Phase B was then carefully dispetsed in Phase A by adding it slowly to Phase A with
oonstant stinting and keeping the temperature at 50C. The resultant mixture of phase B
and phase A was then I IUI "Uy~:l ,;sed with hish shear mixing, and the tesultant w"~"l, .,'~,J
30 emulsion was allowed to cool to ambient temperature under low energy mixing.
The viscosity modifier was then dispetsed in the emulsion under high shear mixing to give a
thickened emulsion.
The above emulsifier ,,u" luuail;ul la E7 to E9 were also fommulated into ~,u,, L_,JUI ~i;l lu Wl l~ .t~
shown in Tables 14 and 17 by mixing the wllluullellll~ in the stated amounts in the above mixing
35 process. The efficacy of each emulsifier composition used in the r,u, ,~"~, d~tla is shown in Tables
12,15 and 18 respectively.
WO95/22897 2 1 838~8 ~ .scl ~u
- 18 -
Table 1 1
Concentnate CE1 ¦ CE2 ¦ CE3
Component .~t./vol of Components
Acetochlor(heroicide) 93%active 5889 5389 5389
Ssfener(~l.,' ' ~inhibitor) ~ 9 529 529
UAY~.,hl) soybean oil 9 159 159
, [~9
8 - 509
9 - 509
propylene glycol 5û9 509 509
10 Rhodopol23(visoositymodifler) 19 19 19
water to 11 to 11 to 11
Table 1
Formulation CE1 ¦ CE2 ¦ CE3
15 Temp.(C) Time(wk) sep2r~tior
O ~'~ N--
22 4 ~ N.. i~
40 4 ~ ~` N~; ~ S
NS = no separation of the emulsion
20 The above wllwl~lal~ were fommulated into wll~auulldillU diluted fonmulations by adding the
~.UI IC~ 1 a~e:a to water with following parameters described above the relevant Tabie in each case
as appropriate: to the given % wt./vol. dilution rate (suitable for the given desired use of the given
(diluted) concentrate), at the given temperature at the given WHO standard hardness of 342
ppm, and with the formulations being left to stand for the giYen iength of time.
The efiicacy of each emulsifier composition used in the ~UI lWI Ill al~ shown in Tables 11, 14 and
17inthefonmulationsw,,c,auu,,Jil,,u,tothe~u,l-,e,llilc~l,,~isshowninTables13, 16and19
respectively, in which the numbering of each formulation Wl I ~a,UUI I~S respectively to the
numbering of each concentnate, and the figures are the volume of the dispense phase of the
30 concentrate (which oontains the cu" -,uul l~ (a), (b) and (c)) which sepanates from the other
ph~_
~ W0 95/22897 2 1 8 3 8 ~ 8 1~1
,9
',able 13
2 % wt./vol, dilution 22C Standard Water H2rdness 342 ppm
Fommulation CF1 ¦ CF2 ¦ CF3
Temp (C) Time (wk) sc ~aratinn (ml)
0 N~ 0.15
22 ~ Tr ~r~ 0.1 l:
40 ~ TC ~(, 0.1 r-
TC = trace (~ 0.05%) cream separation of the emulsion
C = cream separation of the emu~sion
Table 14
Concentrate CE4 ¦ CE5 ¦ CE6
omponent wt./vol of Compnnents
' r`lfluralin ~heroicide) 96~ active 5005 5009 5009
509
a - 509
_~ , 509
propylene alycol 209 205 209
xylene 2059 2059 2059
water to 11 to 11 to 11
Table 15
Fommulation CE4 ¦CE5 ¦CE6
Temp ('C) Tlme ~wk) ~i~DaratiDn
0 \` ~.. NS
22 4
40 4
NS = no separation of the emulsion
1~
30 2 % wt IYOI~ dilution 22C Standard Water Hardness 342 ppm
Fommulation CF4 ¦CF5 ¦CF6
Temp (G) Tme (wk) ! epqratiol ~ml)
0.2 - 0.~5C 0.6C
22 4 o.2 C O.fi C
40 4 0.3.'~C 0. ~ C
35 C = cream separation o~ the emulsion
WO 95122897 2 1 8 3 8 5 8
- 20 -
oncentrate CE7 ¦ CE8 ¦ C 9
r.omponent v,t./vol of Comp~nen
'u~uiw,,i~ule(fungicide)60%active 4179 4173 4~ g
1 009
r~ - 100g
g ~ 009
propylene glycol 1009 1009 ~ ûug
xylene 1839 1833 ~.,9
~vater to 11 to I to I
rable 1
Formulation CE7 ¦ CE8 ¦ CE9
Temp (C) Time (wk) sep~-~tior
0 ~ N~
15 22 4 ~ ~ N-
40 4 '~ ` N~
NS = no separation of the emulsiûn
20 2 % wt./vol. dilution 22C Standard Water Hardness 342 ppm
Fommulation CF1 ¦ CF2 ¦ CF3
Temp (C) Time (wk) se~ara ion (ml)
û ~ 2 C
22 4
40 4 ~ TC 1 C
C = cream soparation o~ the emulsion
I = impossible to emulsify
