Note: Descriptions are shown in the official language in which they were submitted.
2~ q239~
.
BIOCIDAL COMPOSITIONS
E~CKCROUND OP TEIE INVI~ WII
1. Field oi the rnventiOn
The present invention relates to biocidai ~ np~~ ns, particu-
larly those .~ ail h~ a s~ bllc mixture o~ <:a~ ~' and organo-
tin biocides userul tor ~ ~1h.g materials exposed to an aquatic
This inventlon especially relates to the prevention and
inhibltlon o~ ~oulin~ or marine structures such as boat, ship, o~ other
vessel hulls, piiings, oil weli drillin~ towers, and the Illte by organisms
commoniy round in sea water.
rn a prererred . 1~ t, the present invention relates to a
biocidal ~ ~ti-~ c.~ a synergistic mixture ot ~;al -te
and tribuqitin biocides. In this prererred t, a marine
structure ~s treated by coating the surtace thereo~ with a paint con-
taining an organic binder and a blocidaiiy et~ective amount o~ the
mixture o~ (1) the s ~ ~ , such as one seiected trom the
group consistin~ o~ 3-iodo-2-propynyl propyl ~e 3-iodo-
2-p~opynyl buql c~ L - t~, 3-iodo-2-propynyl hexyl Ca~ i
3-lod~2-propynyl ~ a~' ~, 31~2 ~..1.,..~1 phenyl
- ~, 3-lodo-2-propynyl benzyl carbamate, 4-iodo-3-buqnyl
propyl Ca~ and mi~ctures thereo~, and (2) the tributytin com-
pound, sUCil as on~ selected trom the group consistlng o~
bis(tribuqltin) oxide, tributyltin rluoride~ tributyltin -- ~ e~
tributyltin phosphate and tributyltin ~ , and mixtures
thereo~. rn another Pmh~iim~r~t a marine structure is treated by
coating its surrace with a . ~....lailli~ a biocidaliy et~ec-
tive amount o~ either 3-iodo-2-propynyl propyl ~alLamate or
4-iodo-3-butynyl propyl cârbamate or a miYture thereo~.
21 92395
-2
2. ~escriPtlon of Related Art
Slnge~ U.S. Patent 3,923,870 describe~ urethanes of l-halogen-
~7~ tit~ted alkynes and their ~ungicidaL actlvity. The compound
3-iodo-2-ptopynyl butyl carbamate (IPBC) (CAS 55406-53-6) described
in U.S. Patent 3,923,a''0 is widely used as a ~ungicide ror aqueous and
organic ~iolvent based sy~items such as paints and coatings, metai cut-
ting iluids, textile and paper coatings, ~nks, plastics, adhesives and
the like. Research indicates that IPBC has a promising ef~icacy pro-
file against wood destroying otganisms (fungi), having shown low toxic
values for common ~ungi. ~ndeed, a unique chdl ~t L~Llc O~ IPBC is
Its e~ricacy against both ~lue stain (~ ~...te~) and generai wood
destroyine ~ungi (t--' ' ~ t~ at a re~--OLI~ A~r~ At1on rate.
IPBC i~i also known as an al~iclde rOr use in ~re~h water and marine
~"At~ons, see U.K. Patent 2,138,292.
It also is known that or~anic tin; such as those or
the ~eneraL rormuia:
(CH3CH2CH2CH2)3 Sn-R4
where R4 is selected rrom (CH3CH2CH2CH2)3SnO, rluoride, chiot~de,
phosphate, acrylate ~lat." r,-l-l.LI,~ , hydro~ide, octoate,
phthalate, suifate, maleate, rumarOte, laureate, linoledte, atietate,
,_~ il.1....,_t~-, and the IDce can be used iri paints to provide
Onti r-aulll.~ property to coOtings appiied to ship hulis to prevent roul-
ing ty a~ae and other marine ot6~anisms (pests~.
Th~ prlor art, however, does not provide any indication
whether the ~ ' ' o~ the run~iclde IPBC or other related
c~; run~,icides with an or6~anic tln compound such as one or
more o~ the d~.~ n~ Jt~ltla r~ , wouid t)e
usetui ror anti-rouline coatines ror l,lvl~_Lh~ materials e~posed to an
aquatic (ee. marine) e.. .Lun~ ~ , such as ship huLls and othe~ under-
water~ ,u.~iu-~.
The erowth ot marine or~,anisms on the ,~l parts o~ a
shiprs huLi ~ncreases the rrictional resistance ot the huL to passage
throu~,h water, leading to increased ruel .~ol~ul.~llua and 'or a reduc-
tion in the speed oi the ship. Marine erowths a~ so rapidly
~ 21 92395
that the remedy ot cleaning and repainting as recuireci in drydock is~eneraliy ~v.~ld .~-i too expenslve An aiternative which has been
practiced with increasing el~iciency over the years, is to Umlt the
extent or ~ouUni~ by applyini~ to the huli a top coat paint incorpo~at-
ing anti-~ouUng agents. Ths anti-rouUng a~ents are blocides which
are ~reed Irom the surface of the paint over a period or time at a
concentration lethai to marine organisms at the hul;i surface. The
anti-~ouUng paint faiis oniy when the cvl.o~ Ldth.,. o~ biocide avail-
able at the paint sur~ace ~alls below the lethal concentration and with
modern paints up to two years of use~ul Ufe is expected.
There are marked ~ tl ~ .c between the requirements ~or
biocides in dif~erent ell~lr~ ta, such as antifuni~al agents in house
paints, fresh water aii~icides, and ~ ro~ agents ~or marine struc-
tures exposed to sea water ~lora and fauna. ~s is i~nown, the miidew
or ~uni~us which i~rows on house paints and the Uke, utiiizes the paint
medium as a nutrient, or in some cases, the ~..1 .1~ substrate, such
as wood, as the nutrient. The myceUa and ~ruiting bodies of the ~ungi
contact or penetrate the paint ~ilm and thus, through intimate con-
tact with any ~uni~icides in the ~iim (to a iari~e extent regardiess o~
whether the ~ungicides are hi~itiy soluble. sllghtly soluble, or insoluble
in water), the rungi are destroyed. In cooUng towers utilizing (resh
water, siime and algae may develop it ef~ective ~ ror com-
battin~ their ~rowth are not present. ~n the case ot cooiing tower
water, the com~ound shouid be highiy soluble. In paints such as exte-
rior house paints, ~ g~lad normal exposure to weather, the solubii-
ity ot the compound is not as criticai since the paint ~iim is oniy spo-
radicalLy exp~xed to iiquid water.
Whiie IPBC and related carbamate ~ are known to
exhibit ~ood ~ungicidai and aii~icidai activity, it is not icnown whether
these runi~Lcides couid aLso be used in anti ~ ~ coatings in combi-
nanon witit i~nown organic tin ~ ~ parncuLarly ~ u~ltlll-
type ~ 1~ . to preYent the ~rowth o~ marine organisms ULce
aigae, barnacLes, ~ h~ bryozoan, tunicates, hydroids, adherent
sUme or other hii~her deYeloped ~., on auiJu~ i sur~aces.
Resuits obtained with anti-~ouUng painu when utiiizin~ iP~C and
_, . .. . . . _ _ _ _ _ _ _ _ _ _ _ _ _ .. . _ _
2l 92395
4 -
related ~ , are not y~ rom their er~ac~l~_..~ as
general blwlGes, whether against bacteria, ~un~i, Insects, etc. ~t also
is not known ir or how lonz the ~ ~' would retain its e ~icacy
as an ~ntl ~uuL~ biocide rG- ~-t1nn or whether it might eYen ~e
superior in overaLt perrormance as an anti-foulin~ compound ~n com-
parison to the ludu~u~uy~l~yl ~;~L - -t~ r~lneC or the
l-i~ulyllll~ t by tl~
~ flt1nn~1y, it is not known how the ~ ' t1nn o~ one or
more members ~rom each group o~ these ~ u~ would a~ect
their overaLt biocidal (anti-~oulin~) activity, ~or example, ir used in
paint to protect ship huLls ~rom the growth ot marine organisms. As
is always a possibitity when using a r ~~ or chemicals having
diverse activities. one or the chemicals may impair or Interrere with
the activity o( the other.
From the ~ore~oing, it is apparent that the er~cctl~.,~ or
biocidal materials userul in ~ ' ~ rungi, insects, bacteria, and
the 18te irl r,u-. aqueous media, and biocides errective in c~mhAttlng
~ungi, slime, and algae in rre3h water systems, carmot be used to pre-
dict the er-e~ ~ or these as dllti ruuL~I~ agents in
sea water and bracldsh water capabb o~ Y~ Llng marine life such
as oarnacles, slime, hydroids, ~gr~ brown relt atgae and the Ltke.
Since the prior art has not disclcsed or sug~ested combining
IPBC or its related carbamate ~ r ~-k with or~anic tin c~
and especiaLty th~ d~U.- t.;LuLylthl t~e biocides, the
prior art doe~ rlot indicate what amounts or the rungicide IPBC (and
it~ related c~ c~ ) and ot the organic tin ~mr~n~1
such as one or more ot the d~U._ ..ut~ tributyltin-type blocides, are
required to provide an optimum in anti-rouling .~ cArl~ against
al~ae and hi~her developed marine u.~ For similar reasons, it
is not known what amounts or IP8C (and its related ca~b~ com-
pounds) and or the organic tin compound are needed to obtain the
lùlU l~lL.~ erricacy needed ror successrul a~ti ~ùul~.t, marine appLi-
cations, or how to ~ormulate an etrective anti-~outant
using this biocide ~omh~nAt1nn
21 92395
rn thi-c regard, there is a ~rowing concern about the environ-
mentat e~rects caused by using the organic tin biocides at their
present commercial leveL as an anti-foulant active ingredient in
coating . rcitinnc ~or aquatic (mar~ne) ~ t has been
shown that, due to the ~ ri use o~ L~i~u~yl~ll, ty~ mp~llnt~c
in partlcular, at Cu~ tlatlu-~ as high asi 20 wt. 96 in paints ror ship
bottoms, the poLiution ot :~UI ~ UUIIIlillg water due to leaching has
reached such a level as to cause the ~ adatlull ol mussel and shell
organismc. These e~ects have been detected along the French-Brit-
ish coastline and a similar ei'iect has been con~irmed in US and ~ar
East waters. Under the most recent regulatory r~triA-tinnc, with lim-
ited ~ c~ pleasure boatsi up to 25 meter_ long are no longer
permitted to use antl-loulant paint containint high levels or
tributyltin I~Mr J
Research has sh~wn that a_ long as the leaching rate o~ tin can
be ~--lnlA ~ at or below about 4 ug/cm2 per day, aquatic li~e does
not appear to be a~ected over the long terr~. However, it has also
been ~ound ti~at to be ei~i'ectiYe- ~or C~J .hu3~4~ marine algae, as well
as higher developed marlne o-~ s, ~rom the painted surilace o~
ship bottoms, a certain minimum leaching rate o~ tirl o~ about 9 to
16 ug/cm2/day is required. UsuaLly, thi~c higher leaching rate is
achieved with a ~ /n 0~ tributyltin compound at about 15%
to 2096 by weight o~ paint.
Obviously, these two ~ui-~T are at odds. Authorities
have lel~ ~la~ agreed that ~ig long a~c there is no SAt~ ul~1 substi-
tute ~or the anti-~oulant or~anic tin actiYe hl~ , . Iar~er ships,
i.e., those above a len~th o~ 25 meters, are stilt permitted to use such
to minimize ~ouling. As an indication o the i . Ia-lc~
o~ new solutions to this a"e old problem, the EPA has agreed to cer-
tii'y within 90 dayg new ann-~oulant paints meeting the l_~lU;l'elYl~
~ '` release rates.
21 92395 ~:
DISCLOSURE OF THE INVENTION
5 According to an aspect of the present invention a method for retarding fouling of an
d~l W~ l surface of a marine structure by marme pests which comprises applying acoatmg of a paint to the surface, the paint containng a biocidally effective amount of
3-iodo-2-propynyl propyl ca~bamate, 4-iodo-3-bytynyl propyl carbamate and mixtures
thereof in admixture with a solvent and a binder.
According to amother aspect of the invention a method for retarding fouling of an
under~vater surface of a marine structure by marine pests which comprises applying a
coating of a paint to the surface, the paint containing a biocidally effective amount of
3-iodo-2-propynyl propyl carbamate in admixture with a solvent amd a binder.
According to yet another aspect of the invention a method for retardirlg fouling of an
l..ll.i~l W~ l surface of a marine structure by marine pests which comprises applying a
coatmg of a paint to the surface, the paint containing a biocidally effective amoumt of
4-iodo-3-butynyl propyl carbamate in admixture with a solvent amd a binder.
DETAILED ~ESCRIPTION OF THE PREFERRED ES~BODIMENTS
Sn ~ , ~ ~ ~ wlth the present invennon, a biocldal compasl-
tlon Is provlded whlch is uselul ror ~.,t~ ~ ~rraces such a~ w~od
and other m~tcslals e~po6ed to an aquaac (marlne) c...;r~ nt trom
25 att~ck by ma~le S~st~. Sn the tirst aspect o~ the inventlon, the com-
podtlon contains ~l synergi5tic mixture of
a) at least on~ 5~ ../I c.. ~- compound havin~ a
rOrmula:
t~C ~ C-~CH~)n-O-C-lnl]mR
In whlch m is 1, 2 ~ 3: n 5 1, 2 or 3; and R Ss hydrogen (H); an
tu~ed or s~ aSXyl, aryl, aralkyl aSkylaryl, aSkenyl,
cycloaSkyl, or ~.,lo~ I or an alkoxy aryl a~l hav~y trom one to
2l~23q~
not more than 2 0 carbon atoms, and m and n may be the
same or different, and
b) at least one trihydrocarbyl tin ~ 1 having
a f ormula:
S F~2
Rl- n_R~
R
10 where Rl, R2 and R3 can each be an alkyl or cycloalkyl
having ~rom l to 6 carbon atoms or an aralkyl or alkaryl
having from 6 to 12 carbon atoms and R~ is selected from
(r~r~r~T~r~2)3Sno~ fluoride, chloride, phosphate, acrylate,
methacrylate, naphthenate, hydroxide, octoate, phthalate,
15 sul~ate, maleate, fumarate, laureate, linoleate,
abietate, and ethAr- lrh~nAte having a weight ratio of
carbamate to trillydLv.iaLlyl tin o~ rrOm about 1:10 to
10:1.
Suitable R substituents for the iodoalkynyl
20 carbamate _ __ ' include alkyls such as methyl, ethyl,
proply, n-butyl, t-butyl, pentyl (amyl), hexyl, heptyl,
octyl, nonyl, decyl, dodecyl, octadecyl, cycloalkyls such
as cyclohexyl, aryls, alkaryls and aralkyls such as
phenyl, benzyl, tolyl, cumyl, hAloqonAted alkyls and
25 aryls, such as chlorobutyl and chluLv~ ..yl, and alkoxy
aryls such as eth~,Ay~ 1 and the like. Thus, suitable
aLl,a~ate: '- are sel ected from the group
consisting of 3-iodo-2-propynyl butyl ~arL~ate (IPBC),
3-iodo-2 ~Lv~yllyl hexyl carbamate (IP~C), 3-iodo-2-
30 propynyl cyclohexyl carbamate (IPCC), 3-iodo-2-propynyl
phenyl v aLLa~ te (IPPhC), 3-iodo-2-propynyl benzyl
carbamate (IP Benzyl C), 3-iodo-2 PLV~YIIY1 propyl
_~L~a~dte (IPPC), 4-iodo-3-butynyl propyl carbamate
tIBPC), 3-iodo-2 ~L~,~y--yl-4-chloro phenyl carbamate
35 (IPClPhC), 3-iodo-2-propynyl-4-chloro butyl carbamate
( IPClBC~ and mixtures thereo~ .
2 ~ 923~5
A preferred group of carbamate fungicides for use
with the trihydroCarbyl tin ~ is represented by
the formula:
~: C-~CN2~,1-O-C-!15--
.,
2 ~ 923 95
~.
g
where n is 1 or 2 and R is propyl, butyl, hexyl, cyclohexyl, phenyl or
benzyl.
Two lodoaLkynyl carbamate c ~ l-u~ , which haYe surprislng
erricacy for controLling rouling of marine structures when used alone,
when used in combination or when used in admlxture with trihydro-
carbyl ffn ~IA~ are 3-iodo-2-propynyl propyl carbamate (IPPC)
and 4-iod~3-butynyl propyl carbamate (IBPC).
Suitable Rl, R2 and R3 ~ ror the trillyd.u~.Ll,~l tin
~omrlln~e are aLkyis such as methyl, ethyl, propyl, butyl, pentyl
(amyl) and hexyl, cycloaLkyls such as .1~.01le,~yl; aryls, araLkyls, or
allcaryls such as phenyl, benzyl and tolyl. These sub~tituents can aLL
be the same, such as tfibutyl, triphenyl and the lilce or can be dirfer-
ent such as die~ lbul~l, dlel~ L~ diamylmethyl, ~Ipl.
eLll~Rlipl-e--~l and the Llke. Suitable lLih~ uC~byl tin ~ ru ~
include Lll~.~.lulle~l tin chloride, tributyl tin chloride, trimethyl tin
chloride and triphenyl tin chloride. Pre~erred l~ d~ L~I tin com-
pounds are selected rrom the group Or tributyltln ~A r~ consist-
ing or bis (tributyltin) oYid~ (TBTO), tributyltin rluoride (TBTF),
tributyltin n._.l-~.. rl.~te, tributyltin rhnerh~, tributyltin
naphthenate and mixtures thereor.
GeneraLly, the ~ riv j or the present irYentlon are for-
mulated as paints lacquers, stains, enamels and the L~ke, hereinarter
reierred to genericaLLy as "paint", and wiLL include a liquid vehicle
(solvent) ~or dissolving or ~ the actiYe biocidal ingredients
and an organic binder. The vehicle may typicaLly contain at least one
Or a diluent, an emulsirler and a wetting agent.
Any conventional organic blnder may be utilized In marine
anti-rouling paint ill~u~ tlllg the biocidal ~ - ~ ' or the
present invention and particularly the ~ .lc anti-foulant mix-
ture Or the present invention. Examples Or ~L~ r~Cusl~el binders
are polyYinyl chloride resins in a solvent based system, chlorinated
rubbers in a solvent based system, acryLic resins and methacrylate
resins ln solvent based or aqueous systems, vinyl chloride-vinyl ace-
tate copolymer systeme as aqueous ~ or solvent based sys-
tems, butadiene ~u~l~ such as ~ ..di_..~ re-lè rubbers,
.. _ .. _ . . . . . .. _ . _ _ _ .
21 92395
- 10 -
a~lu.-ltrile rubbers, and bul~ y~ a.lJlOI ilrile
rubbers, drying oils such as linseed oil, alkyd resins, asphalt, epoxy
resins, urethane resins, polyester resins, phenolic resins and the like.
The paints commonly may contain inorganic pigments, such as
titanium dioxide, rerric oxide, silica, talc, or china clay, organic pig-
ments such as carbon black or dyes insoluble in sea water, and may
contain materials such as rosin to provide contro~led release oi' the
anti-roulant, rosin being to a very slight extent soluble in sea water.
The paints may contain plasticizers, rheology cl~ ic modiliers
and other conventionai 11.$., " '~
In still other aspects or the present invention, the composi-
tions, par~ l.. ly when ~u.. la~ as paints, also are provided with
other ad~uvants ~v..v~lltlu..ally employed in compositions used ror
ting materials exposed to an aquatic c:llvl-u-~. .t such as addi-
tional ~ungicides, auxiliary solvents, processing additives such as
deloamers, rixatives, ~ , UV-stabilizers or stability enhanc-
ers, water soluble or water insoluble dyes, color pigments, slccatives,
corrosion inhibitors, i ' or a~ t agents such as
...y~.e.l.yl cellulose, polyarcylic acid or puly ~~h~^rylic acid,
anti-skinning agents and the like. Additionai rungicides used in the
C~ L~-~c~ are pre~erably soluble in the liquid vehicle.
The synergistic biocidal ~nmrcit1nn or the present inveQtion
generally comprises rrom about 0.1 to 10 parts by weight, more gener
ally rrOm about 0.2 to 5 parts by weight, and most Orten irom about
0.3 to 4 part by weight Or at least one ~-il-~J~ 1 tin ~mrl~n~i,
r~ d~ one selected rrOm the group consi5ting Or bis(tributyltin)
o~de, tributyltin fluoride, tributyltin rr-t~- ~lalc:, tributyltin phos-
phate and tributyltin nqrhthPnotP and mi~tures thereof per part by
weight Or the iodoalkynyl carbamate c . i, with the carbamate
compound prererably being selected rrOm the group consisting Or
3-iodo-2 ~ uylljl tul~l carbamate, 3-iodo-2-prownyl hexyl
carbamate, 3-iodo-2-propynyl ~ yl carbamate, 3-iodo-2-pro-
pynyl phenyl rorb~motP, 3-iodo-2-propynyl benzyl carbamate,
3-iodo-2-propynyl propyl carbamate, 4-iodo-3-butynyl propyl
2~ 92395
11
...a~e, 3-iodo-2 p-u~yll~l 4 ~I-loro phenyl carbamate,
3-lodo-2 ~ù~y~ l 4 cl-loro butyl carbamate and mixtures thereor.
C~mrncit~nnc o~ the present invention can be provided as a
ready-~or-use product in the orm or aqueous solutions and disper-
sions, oil solutions and ~ iulls, emulsions, aerosol preparations and
the like or as a CU~ . The concentrate can be used as is, for
example as an additive ~or paint, or can be diluted prior to use with
additionai solvents or ~ L~ g agents.
When the cnmrc~Si~lnc are supplied as a concentrate with the
active ir";.èdle-lla dissolved or dispersed in a iiquid vehicle or carrier
material, the active biocidal ingredient or mixture of ingredients typi-
cally comprises Irom about 0.1% by weight up tû about 80% by weight
oi the total composition. Arter ~ t~nn as a paint, the prepara-
tion typically wi~l contain rrom about 0.1% by weight up to about 40%
by weight, more general~y rrOm about 1.0% to about 20% by weight,
and mo~ct o~ten rrom about 1% tû about 10% by weight of the active
ingredient or mixture of active ingredients. A liquid vehicle normally
comprises more than about 70% by weight, and more generally above
about 90% by weight of the ~ r~ ] ~ when it is rormulated as a
paint. In some ~ ateS, however, the liquid vehicle can consti-
tute as little ac 5% by weight of the ~ "p~
The liquid vehicle is not a criticai aspect of the present inven-
tion and any liquid which does not interfere with the biocidal activi-
tie_ oi' the active In~ ' and which is ~omr~tihl~ with the dis-
ciosed ,,~ c potentialiy can be used in the present invention.
Suitâble materiais ror the iiquid vehicle include water and organic
solvents including aliphatic l~yd~ ..bu-~, aromatic l-ydl~ lbul~,
such as xylene, toluene, mixtures or aliphatic and aromatic hydrocar-
bons having boiling points between 100 and 320C, prererably
between 150 and 230C; high aromatic petroleum distillates, e.g.,
solvent naptha, distilled tar oii and mixtures thereof; alcoho-s such as
butanol, octanol and glycois vegetable and mineral oils; ketones such
as acetone petroleum ~ractions such as mineral spirits and Icerwene,
chlorinated ll~d~ a.lJo-b, glycol esters, glycol ester ethers, and the
like. The liquid vehicle may contain at least one polar solvent, such
.. _ .. _ ., . . . , . . _ . _ _ _ _ . _ _ _
21 92395
- 12 -
as water, in admlxture with an oiiy or oil-like low-volatility organic
solvent, such a_ the mlxture or aromatic and aliphatic solvents ~ound
in white spifits, also commonly called mineral spirits.
The liquid vehicle also may commonly include an emulsifier, a
wetting agent, a dispersing agent or other surrace active agent.
Examples o- suitable ~ ~,JIciri~ ~ are the nu--y~ è~lol ~tllylel~e oxide
ethers, and pOlyu~Lye~ lel~è sorbitd esters or ~ulyu~Lyetllylelle
sorbitan esters Or ratty acids. For example. a userui formulation may
contain the mixture or the active biocidal ~nnctituPntc dissolved in an
ori~anic solvent such as mineral spirits which iQ turn is emulsiried
with the aid o~ a suitable emulsirier in water as the primary liquid
vehicle.
An aerosol preparation according to the invention is obtained
in the usual manner by illcùl~v~alll~ the active ingredients dissolved
or suspended in a suitable solvent, in a volatile liquid suitable ror use
as a propellant, ror example the mixture or chlorine and ~luorine
defivatives o~ methane and ethane commerciaiiy available under the
trademark "Freon", or r ~ air.
The balance o~ the; I, ' may include additional ingre-
dients known to be use~ul in preservatives and coaffngs ror aquatic
applications and related products. Such ingredients include ~ixatives
such as ~;a.bu~yl~rthylcellulose~ polyvinyl alcohol, a pararrin and the
like, c~ ~IvèllL~, such as ~ yl~ 1 acetate and ~ .I-u~y~ l ace-
tate and ~ _IJ- 1~ ~ such as benzoic acid esters and phthiates, e.g.,
dibutyl phthalate, dioctyl phthaiate and didodecyl phthalate. Option-
ally dyes, color pigments, corrosion inhibitors, chemicai st~hil~7Prs or
siccativeC (dryers) such as cobalt octate and cobalt n~rhthPn ItP also
may be included depending on speciric Irrl~at~nnc
Such additionai Ill,sl~i;el.t~ are not essential to the practice Or
the present invention but are included in particular rormulations to
optimize overali e~(~_Ll~e~ea~ and ease d arp~ t~nn The specLric
examples o~ suitable ~J--~LItL_..L~ for specii'~c preparations as enumer-
ated above are not meant to be lim~ting and a wlde variety o~ other
possible ill!LLeliellL~ wiLi be l~c~ ed by those skiLied in the art.
Simiiarly, the quantity o( such additional ingredients in any
. , .... .. . . _ .. . .. . . .. _ _ _ _ _ _ . _ _ .
2~ 92395
- 13 -
formulation is not critical. They generally can be used in an amount
conventionally employed ~or products designed to be used in applica-
tions lar protecting materials exposed to an aquatic environment.
Normally, the totally ~ormulated c~nr~ , may contain from about
0.1% to 95% by weight, and more usually from about 1% to 50% by
weight o~ these additional i~ on a totai solids basis.
Biocidal compositions ol the present invention can be applied
by any of the t~-~hniqll~c known in the art including brushing, spray-
ing, roll coating, dipping and the like. Generally, to obtain ef~ective
t, it should be surficient to apply the ~ r~ in an
amount to provide between about 20 to 180 grams o~ the active ingre-
dient or mixture o~ active illt~ per square meter o~ surlace
area to be treated (about 0.0040 to 0.037 pound per square ~oot), with
an amount o~ about 80 to 120 g/m2 (about 0.016 to 0.025 lb/~t2) being
more typical. or course, higher rates or ~rr'i~lti~n can be used ir
desired.
cnm~nC;tinnC Or the present invention can be prepared simply
by mixing the various ~ tc at a ~ e-~ lu--~ at which they are
not adversely arfected, e.g., at a temperature of from about -5C to
80C, preferably at a ~Lupe.~ ~u-e Or ~rom about 10C to 45C and at
a pressure Or 450 mmHg to 900 r~mHg, preferably at a~out 650 mmHg
to 850 mmHg. Preparation conditions are not critical. Equipment
and methods Q~ lu..ally employed in the m~nll- ~ule o~ paint and
similar , ' can be .d~ u~l~ employed.
In ,..~ ' ~ testC over a period o~ 7.5 weeks during the sum-
mer, which is a high growing season for marine organisms, test panels
were coatec with a representative paint used as a base for preparing
antl-fouling paintC and were placed in seawater. Ihe base paint was
mixed with the individual rnm[~lln~c listed in the table below up to a
concentration o~ 10 wt. 96. The individual test results are listed in the
lollowint table:
21 92395
- 14 -
Use
ComDound Level 4 Weeks 6 Weeks 7.5 Weeks
TBTO 10% clean clean m. growth
TBTF 10% clean clean m. growth
IPBC 10% clean sl. rowth h. rowth
IPCC 10% clean sl. rowth h.-rowth
IPPhC 10% clean sl. rowth h. rowth
IP Benzyl C 10% clean sl. rowth h. rowth
TBTO/IPBC 5%+5% clean clean clean
TBTO/IPBC 3.5%+6.5% clean clean clean
IBTO/IPBC 3.5%+3.5% clean clean clean
TBTO/IPBC 2%+8% clean m. growth sl. growth
TBTO/IPBC 8%+2% clean clean m. growth
TBTO/IPBC 6.5%+3.596 clean clean clean
Note: m = moderate, sl = slight~ h = heavy
The table shows slight to heaYy growth ~or IPBC and its deriva-
tives, as well as moderate to slight growth ~or the tributyltin deriva-
tives used at a concentration ot 10 wt. % in the paint composition.
A~ter 7.5 weeks, however, in aLi instances the individual biocides
showed signs o( failure at use levels o~ 10 wt. %.
Su.t-6il"~1y, the synergistic . ' o~ the present inven-
tion showed a superior elficacy when used in the same total amount.
Suitable points can be made up using a ratio ot 1 wt. % TBTO and 10
wt. % IPBC up to 10 wt. % TBTO and 1 wt. % IPBC. Primarily, when
IPBC and TBTO were used in a ratio o( 1:4 to 4:1 the mixture showed
excellent performance with an optimum close to a ratio or 1:1 ~y
weight.
With a second test series the ratio Or 1:4 to 4:1 was evaluated
in ~.~ln~ total amount o~ the sum of both biocides. Even at a
totai Or ~% or active ingredient pre~erably in the ratio or 1:1 added to
a standard coating (paint) ~or ship bottoms, the ~.5 week test period
contlnued to indicate superior activity, in ~ ~-- to TBTO at a
higher level. These ~. L5 clearly show that the combination o~
IPBC and TBTO is more efrective than IPBC or TBTO applied on their
own as anti-~ouiing biocides, indicating a synergistic ef~ect.
Prererably, the two ~ ..~ are premixed berore use to
~orm a concentrate in the ratio or 1:4 to 4:1 in a concentration up to
a totai or 80% dissolved in suitable auxiiiary solvents like Xylol or the
_ _ _ _ _ _ _ _ _ , _ _ . _ _, _ . . .
21 92395
- 15 -
like to provide easy and ~ùm~ eùu~ dl~llibu~lu~ in the paint, which
is intended to perform as an anti-fouling coating.
The (ollowlng examples are illustrative ot cù-npo~ltlu--a accord-
ing to the present invention and are not intended to be limiting.
ExamDle 1:
3-iodo-2-propynyl butyl carbamate 5%
tributyltin oxide s%
auxiliary solvents 3.3%
vlnyl acrylic paint 86.7%
Example 2
3-iodo-2-propynyl butyl carbamate 4%
bis (tributyltin) oxide 5%
auxiliary solvent 4%
vinyl acrylic copolymer paint 87%
ExamDle 3:
3--iodo--2--pro nyl butyl C<~-IJdl-ld~ 3.5%
bis (tributyl$ oxide 3.5%
auxiliary solvent 3,0%
vinyl acrylic paint 90.0%
Exam~le 4:
3-iodo-2-propynyl butyl carbamate 6%
bis (tributyltin) oxide 3.5%
auxiliary solvent 3.3%
vinyl acrylic ~u~l,~ paint 87.2%
ExamDle 5:
3-iodo-2-propynyl butyl carbamate 4%
bis (tributyltin~ oxide 4%
auxiliary solvent 4%
oil based aLkyd resin paint 88.0%
ExamDle 6:
3-iodo-2-propynyl butyl ~ d---ale 5.0%
bis (tributyltin) oxide 5.0%
auxiliary solvent 4.0%
pigments 10.0%
epoxy based paint 76.0%
2 1 923 95
.
- 16
ExamDIe 7:
3-iodo-2-propynyI buty1 carbamate 4.0%
bis (tributyltin) oxide 6.0%
auxiliary solvent 3.0%
pigments 10.0%
chlofinated rubber based paint 77.0%
ExamPle 8:
3-iodo-2-propynyl butyl carbamate 5.0%
bis (tributyltin) oxide 5.0%
auxiliary solvents 5.0%
acrylic based paint 85.0%
Example 9:
3-iodo-2 ~ yI butyl carbamate 6.0%
tributyltin oxide 4.0%
auxiliary solvent 6.0%
urethane based paint 84.0%
While certain specific . ,l~llm ..~ of the invention have been
described with particularity herein, it wili be .~ i that various
m~i~ 3tinn.c thereo~ will occur to those skilled in the art and it is to
be ~ ~i that such m~~ t;l-ne and variations are to be
include~i within the purview of this ~rr~ ti~n and the spirit and
scope o~ the appendeli claims.
