PO01 00530-Foreign Countries
F k . mulations comprising stabilized iodine-containing compounds
The invention relates to compositions comprising a) microcapsules comprising at least one iodinecontaining
biocide and b) at least one nitrogen-containing inorganic carrier material, to a process
for producing the compositions according to the invention, and to the use of the aforementioned
5 compositions for protecting industrial materials, such as in particular coating compositions and the
proLected industrial materials themselves.
Iodine-containing biocides are used widely for protecting industrial materials such as for example
coating compositions for avoiding infestation, decomposition and visual alteration by fungi,
bacteria and algae. Moreover, iodine-containing biocides, also in combination with biocides of
10 other active ingredient classes, are used as a component of biocidal mixtures, for example in wood
preservatives.
A common feature of the iodine-containing biocides is that, upon exposure to light, they are
decomposed even without dilution or in solutions or mixtures, which typically leads to yellowing
and a reduction in effect or even loss of effect.
15 These properties hinder or prevent the use of iodine-containing biocides in areas of application
where a high colour stability is a prerequisite for marketability, such as for example in light, or
white coating compositions; see in this regard also WO 00/16628 A.
Furthermore, many iodine-containing biocides, in particular iodoalkynyl compounds, are
decomposed particularly rapidly by metal compounds and as a result become ineffective. This
20 property prevents their use in coating compositions based on organic solvents since these are
typically equipped with transition metal compounds such as cobalt, lead, manganese and vanadium
compounds as siccatives in order to ensure rapid drying.
Within the context of the invention, coating compositions include protective compositions,
coatings and coating compositions, such as, for example, paints, varnishes and stains, primers and
25 impregnation systems.
Furthermore, the aforementioned compositions can comprise transition metal compounds which
act as colour-imparting pigments and sometimes exert a comparable destructive effect on the
iodine-containing biocides.
Besides the siccatives and pigments, a series of other constituents such as processing additives,
30 plasticizers, anti-settling agents, thixotropic agents, corrosion inhibitors, skin preventers and
PO0 1 00530-Foreign Countries
bi Iars are typically used for producing the aforementioned compositions; these may w lead in varying intensity to a decomposition of iodine-containing biocides.
Besides the protective compositions, coatings and coating compositions based on organic solvents,
the use of iodine-containing biocides in certain water-based compositions is also problematic. If,
for example, the film formation and film curing of a water-based coating composition is based on
the oxidative crosslinking of water-soluble or dispersed alkyd resins, then transition metal
compounds are used as siccatives in these systems too, and their use is associated with a
decomposition of the iodine-containing biocides present.
Methods and compositions for preventing the degradation of iodine-containing biocides in alkydresin
paints based on organic solvents and containing transition metal compounds are already
known from the prior art.
Thus, for example, WO 98122543 A describes the addition of chelating reagents, and patent
specifications WO 00f 16628 A, US 4,276,211 and US 4,297,258 describe the addition of organic
epoxides.
It is known fi-om EP 083 308 A to suppress the light-induced decomposition of iodopropargyl
butylcarbamate by adding tetraalkylpiperidine compounds or UV absorbers.
According to W0 2007/028527A, iodine-containing biocides are stabilized with 2-(2-
hydroxypheny1)benzotriazoles.
Furthermore, synergistic mixtures of epoxides and UV absorbers (see W0 99129176 A) or
benzylidene campher derivates (US 6,472,424) have also been described which are said to lead to
reduced yellowing.
Moreover, WO 20071101549 A describes the stabilization of iodine-containing biocides by means
of azole compounds, and WO 20 1011 123 87 A describes the stabilization of iodine-containing
biocides by means of aziridines.
However, the effect of the aforementioned stabilizers is not always adequate and is encumbered
with application-related disadvantages. Thus, in particular, the drying times of coating
compositions are often considerably extended, and in many cases this is unacceptable to the user.
Moreover, the inhibition of discoloration is not always adequate.
PO01 00530-Foreign Countries
3 therefore the object to provide compositions which have the excellent biocidal effect of
It 1"
iodine-containing biocides and nevertheless have good application properties such as rapid drying
times and colour stability.
Compositms have now been found which satis@ these requirements.
5 These compositions according to the invention comprise
rn microcapsules comprising at least one iodine-containing biocide
rn at least one nitrogen-containing inorganic carrier material
rn optionally, but preferably at least one nonpolar solvent.
The scope of the invention includes the radical definitions and/or parameters listed above and
10 below, in general terms or in preferred ranges also in any desired combination with one another.
The microcapsules
The compositions according to the invention comprise microcapsules comprising at least one
iodine-containing biocide. Within the scope of the invention, microcapsules are to be understood
as meaning particles with a particle size of 100 nm to 500 pm in which at least one iodine-
15 containing biocide is surrounded by a capsule material. According to the invention, the
compositions preferably comprise microcapsules with a weight-average particle diameter of 1 pm
to 100 pm, particularly preferably 2 pm to 75 pm.
The content of the microcapsules comprising at least one iodine-containing biocide of at least one
iodine-containing biocide is for example 1 to 90% by weight, preferably 20 to 85% by weight.
Iodine-containing biocides are to be understood as meaning compounds which carry one or more
iodine atoms and have a biocidal effect.
Preferred iodine-containing biocides are for example those which are selected fiom the group
consisting of: diiodomethyl p-tolyl sulphone, diiodomethyl p-chlorophenyl sulphone, 3-bromo-2,3-
diiodo-2-propenyl alcohol, 2,3,3-triiodoallyl alcohol, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-
iodo-3-pyridiny1)methoxyl-3(2H)-pyridazinone (CAS RN: 120955-77-3), iodofenfos, 3-iodo-2-
propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl 4-chlorophenyl formal (IPCF),
N-iodopropargyloxycarbonylalanine, N-iodopropargyloxycarbonylalanine ethyl ester, 3-(3-
iodopropargyl)benzoxazol-2-one, 3-(3-iodopropargy1)-6-chlorobenzoxazol-2-one, 3-iodo-2-
propynyl alcohol, 4-chlorophenyl 3-iodopropargyl formal, 3-iodo-2-propynyl propylcarbamate,
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3-,go-2-propynyl butylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo-2-
propynyl phenylcarbamate, di(3-iodo-2-propynyl) hexyldicarbamate, 3-iodo-2-propynyloxyethanol
ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate, 3-iodo-2-propynyl
thioxothioethylcarbamate, 3-iodo-2-propynyl carbamate (PC), ' 3-bromo-2,3-diiodo-2-propenyl
5 ethylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate and 3-iodo-2-propynyl cyclohexylcarbamate.
Particularly preferred iodine-containing biocides are for example those which are selected from the
group consisting of 3-iodo-2-propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl
4-chlorophenyl formal (IPCF), N-iodopropargyloxycarbonylalanine,
N-iodopropargyloxycarbonylalanine ethyl ester, 3-(3-iodopropargyl)benzoxazol-2-one,
10 3-(3-iodopropargy1)-6-chlorobenzoxazol-2-one, 3-iodo-2-propynyl alcohol, 4-chlorophenyl
3-iodopropargyl formal, 3-iodo-2-propynyl propylcarbamate, 3-iodo-2-propynyl butylcarbamate
(PBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo-2-propynyl phenylcarbamate,
di(3-iodo-2-propynyl) hexyldicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbamate, 3-iodo-2-
propynyloxyethanol phenylcarbamate, 3-iodo-2-propynyl thioxothioethylcarbamate, 3-iodo-2-
15 propynyl carbamate (PC), 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 3-iodo-2-propynyl
n-hexylcarbamate and 3-iodo-2-propynyl cyclohexylcarbamate.
Very particularly preferred iodine-containing biocides are for example those which are selected
from the group consisting of 3-iodo-2-propynyl propylcarbamate, 3-iodo-2-propynyl
butylcarbamate (IPBC), 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo-2-propynyl
20 phenylcarbamate, di(3-iodo-2-propynyl) hexyldicarbamate, 3-iodo-2-propynyloxyethanol
ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate, 3-iodo-2-propynyl
thioxothioethylcarbamate, 3-iodo-2-propynyl carbamate (PC), 3-bromo-2,3-diiodo-2-propenyl
ethylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate and 3-iodo-2-propynyl cyclohexylcarbamate.
Further iodine-containing biocides are for example compounds of the formula (I)
in which
R' is unsubstituted or substituted alkyl, alkenyl, alkynyl or phenyl,
where the compounds of the formula (I) are preferably those in which
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R is straight-chain or branched C1-Cs-alkyl which is unsubstituted or mono- or
polysubstituted identically or differently, a straight-chain or branched C2-Cs-alkenyl
which is unsubstituted or mono- or polysubstituted identically or differently, or straightchain
or branched C2-Cs-alkynyl which is' unsubstituted or mono- or polysubstituted
identically or differently,
where the substituents for the alkyl, alkenyl and alkynyl radicals mono- or polysubstituted
identically or differently are selected from the series halogen; nitro; cyano; hydroxy;
unsubstituted C1-C6-alkoxy; C1-C6-alkoxy, which is mono- or polysubstituted such as for
example entirely identically or differently by halogen; unsubstituted C1-C6-alkylthio;
C1-C6-alkylthio mono- or polysubstituted such as for example completely, identically or
differently by halogen; amino; monoalkylamino with straight-chain or branched C1-C6-
alkyl radicals; dialkylamino with identical or different, straight-chain or branched C1-C6-
alkyl radicals; unsubstituted phenyl; phenyl which is mono- or polysubstituted identically
or differently by halogen, nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio,
haloalkylthio, acyl, acyloxy, alkoxycarbonyl, carboxyl, amino, monoalkylamino or
dialkylamino;
R' is unsubstituted phenyl or phenyl which is mono- or polysubstituted identically or
differently by halogen, nitro, cyano, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy,
alkylthio, haloallcylthio, acyl, acyloxy, alkoxycarbonyl, carboxyl, amino, monoalkylamino
or dialkylamino.
The microcapsules present according to the invention in the compositions comprise at least one,
preferably one or two, very particularly preferably one, iodine-containing biocide. Furthermore,
different microcapsules may be present in the compositions according to the invention which differ
with regard to the one or more iodine-containing biocides present therein.
A very particularly preferred iodine-containing biocide is IPBC. Very particularly preferred
microcapsules are those which comprise IPBC and otherwise no further iodine-containing
biocides, yet further preferred microcapsules are those which, besides the capsule material,
comprise exclusively IPBC as biocide.
Suitable capsule materials are natural, semisynthetic and synthetic capsule materials.
Suitable natural capsule materials are, for example, gum Arabic, agar, agarose, maltodextrin,
sodium alginate, calcium alginate, dextran, fats, fatty acids, cetyl alcohol, milk solids, molasses,
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g e p e , gluten, albumin, shellac, starches, caseinates, stearins, sucrose, and also waxes, such as
beeswax, carnauba wax and spermaceti wax.
Suitable semisynthetic capsule materials are, for example, cellulose acetate, cellulose acetate
butyrate, cellulose acetate phthalate, cellulose nitrate, ethylcellulose, hydroxypropylcellulose,
5 hydroxypropylmethylcellulose, hydroxypropylmethylcellulose phthalate, methylcellulose, sodium
carboxymethylcellulose, hydrogenated tallow, myristyl alcohol, glycerol mono- or dipalmitate,
hydrogenated castor oil, glyceryl mono- or tristearates and 12-hydroxystearyl alcohol.
Suitable synthetic capsule materials are, for example, formaldehyde-melamine resins, acrylic
polymers and copolymers, such as polyacrylamide, polyalkyl cyanoacrylate, and poly(ethy1ene
10 vinyl acetate), aluminium monostearate, carboxyvinyl polymers, polyamides, poly(methy1 vinyl
ether-maleic acid anhydride), poly(adipy1-L-lysine), polycarbonates, polyterephthalamide,
poly(viny1 acetate phthalate), poly(terephthaloy1-L-lysine), polyaryl sulphones, poly(methy1
methacrylate), poly(s-caprolactone), polyvinylpyrrolidone, polydimethylsiloxane, polyester,
polyglycolic acid, polylactic acid and copolymers thereof, polyglutaminic acid, polylysine,
15 polystyrene, poly(styrene-acrylonitrile), polyvinyl alcohol, polyureas and polyurethanes, and
mixed polyurea-polyurethane compounds.
Particularly preferred capsule materials are selected from the group of polyureas, polyurethanes
and mixed polyurea-polyurethane compounds, very particular preference being given to those
polyureas and polyurethanes and also mixed polyurea-polyurethane compounds which are reaction
20 products of
at least one compound selected from the group of polyamines, polyols and amino alcohols
with
at least one polyisocyanate.
Within the context of the invention, polyols are to be understood as meaning compounds which
25 have at least two hydroxy groups, which are bonded in each case to an sp3-hybridized carbon atom.
Preferred polyols are glycerol, pentaerythritol, trimethylolethane, trimethylolpropane and
ethanediol, 1,2-propanediol, 1,3 -propanediol, 1,2-, 1,3- or 1,4-butanediol, diethylene glycol and
neopentyl glycol.
Within the context of the invention, polyamines are to be understood as meaning compounds
30 which have at least two primary or secondary amino groups, which are bonded in each case to one
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spabridized carbon atom, or in the case of secondary amino groups to two sp3-hybridized carbon
atoms.
Preferred polyamines are diaminoethane, diaminopropane, diaminobutane, diaminopentane,
diaminohexane, in each case all isomers, 1,2-diaminocyclohexane, 4,4'-diethylenetriamine,
5 hexamethylenediamine, isophoronediamine, triethylenetetramine and
trimethylhexamethylenediarnine, guanidines. The polyamines can also be used as salts, such as
hydrochlorides, sulphates or carbonates, depending on reactivity.
Within the context of the invention, amino alcohols are to be understood as meaning compounds
which have at least one hydroxy group and at least one primary or secondary amino group, the
10 hydroxy groups and amino groups being bonded in each case to an sp3-hybridized carbon atom.
Preferred amino alcohols are ethanolamine and triethanolamine.
Within the context of the invention, polyisocyanates are to be understood as meaning compounds
which have at least two isocyanato groups (-NCO), which are bonded in each case to an sp2- or
sp3-hybridized carbon atom.
15 Preferred polyisocyanates are aliphatic polyisocyanates such as hexamethylene diisocyanate
(HDI), HDI trimer, HDI allophanate, HDI uretdione, isophorone diisocyanate (IPDI), 1,4-
cyclohexyl diisocyanate (CHDI), or aromatic polyisocyanates such as tolylene diisocyanate (TDI),
diphenylmethane diisocyanate (MDI), or polymeric diphenylmethane diisocyanate (PMDI).
Numerous processes are known for producing the aforementioned microcapsules (see for example
20 CA. Finch, R. Bodmeier, Micro-encapsulation, Ullmann's Encyclopedia of Industrial Chemistry,
6~ Edition 2001, Electronic Release).
The person skilled in the art can in each case select a suitable process by means of a few
experiments depending on the iodine-containing biocide to be used and the capsule material to be
used.
25 The iodine-containing biocides encapsulated with polyurethanes can be obtained for example also
in a manner known per se analogously to the methods given in US 200610251688,
US 200710053950 and Abstract Postersession P 29, XVth International Conference on
Bioencapsulation, Dublin, Ireland Sept. 4-8, 2008. Here, the iodine-containing biocides are
dispersed in an aliphatic hydrocarbon which comprises an amphoteric surfactant, with polyols then
30 being crosslinked with polyisocyanate in the presence of catalyst.
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='@ referred embodiment that is hitherto unknown and therefore likewise encompassed by the
invention, iodine-containing biocides, in particular solid iodine-containing biocides such as, for
example, IPBC, can be advantageously incorporated into microcapsules such that
a) a dispersion of at least one iodine-containing biocide and at least one alkyd resin in a
5 nonpolar solvent is admixed with an emulsion comprising a nonpolar solvent and at least
one compound selected from the group polyol, polyamine and amino alcohols,
b) and the mixture resulting according to step a) is reacted with at least one polyisocyanate in
the presence of catalyst.
The reaction according to step a) preferably takes place in the presence of at least one surfactant,
10 the emulsion particularly preferably comprising at least one surfactant.
A dispersion of microcapsules comprising at least one iodine-containing biocide is obtained
directly in the manner according to the invention.
Within the context of the invention, alkyd resins are to be understood as meaning polyesters which
consist to at least 80% by weight, preferably to at least 90% by weight of structural units which are
15 derived from
polyols and
polybasic carboxylic acids and
saturated or unsaturated, preferably unsaturated C8 to C2~-monocarboxylica cids.
The alkyd resins preferably have a molar mass of 500 to 100 000 g/mol, particularly preferably
20 from 1000 to 50 000 g/mol, in particular from 1500 to 20 000 glmol (determined by laser light
scattering, see for example "Static Light Scattering of Polystyrene Reference Materials: Round
Robin Test", U. Just, B. Werthmann International Journal of Polymer Analysis and
Characterization, 1999 Vol. 5, pages 195 - 207).
Preferred polyols here are also glycerol, pentaerythritol, trimethylolethane, trimethylolpropane and
25 ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, diethylene glycol and
neopentyl glycol.
Preferred polybasic carboxylic acids are phthalic acid, maleic acid, isophthalic acid, terephthalic
acid, trimellithic acid, adipic acid, azelaic acid or sebacac acid, the anhydrides of the
aforementioned acids also of course being used for producing the alkyd resins.
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Pr*d
8 to C2~monocarboxylicac ids are those which are present in linseed oil, oiticica oil,
tung oil, soybean oil, sunflower oil, safflower oil, castor oil, tall oil, coconut oil, peanut oil as
glycerol esters.
In one embodiment, the alkyd resins can optionally also be modified with natural resins, phenolic
5 resins, acrylic resins, styrene, epoxy resins, silicone resins, isocyanates, polyamides,
polycarbamates or aluminium alcoholates.
In a hrther embodiment, the alkyd resins are thixotroped, i.e. are either treated with a thioxotropic
agent or chemically modified such that they have thixotropic characteristics. Such thixotroped
alkyd resins can be obtained for example from the company WorlBe.
10 The nonpolar solvents to be used in the process according to the invention are organic solvents
with a dielectric constant of less than 5.00 at 25OC, in which the iodine-containing biocide used is
insoluble or only slightly soluble, i.e. up to a maximum of 2% by weight, preferably to a maximum
of 0.5% by weight. Such solvents are for example and preferably hydrocarbons such as, for
example, aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, benzine fractions,
15 benzene, toluene, xylene, various petroleum ethers, hexane, cyclohexane, mineral oils, paraffin
oils, such as e.g. isoparaffins, highly aromatic petroleum such as naphtha, but also other petroleum
fractions or mixtures of the aforementioned solvents.
The dispersions can be prepared by standard processes, for example by means of suitable
dispersing devices, but also by grinding the mixture from active ingredient, hydrocarbon and alkyd
20 resin by means of suitable mills.
The dispersion contents of iodine-containing biocides, alkyd resins and nonpolar solvents can be
varied in a wide range according to the invention. In general, the dispersions comprise 2 to 80% by
weight of at least one iodine-containing biocide, 10 to 80% by weight of the nonpolar solvent and
2 to 40% by weight of alkyd resin, the sum of the three aforementioned components being 90 to
100% by weight, preferably 95 to 100% by weight, of the total dispersion. Preferably, the
dispersions comprise 5 to 70% by weight of at least one iodine-containing biocide, 20 to 60% by
weight of the nonpolar solvent and 4 to 30% by weight of alkyd resin, the sum of the three
aforementioned components being 90 to 100% by weight, preferably 95 to 100% by weight, of the
total dispersion.
30 The dispersions can be prepared by standard processes, for example by means of suitable
dispersion tools, but also by grinding the mixture of active ingredient, hydrocarbon and resin by
means of suitable mills.
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TI- mulsions to be used according to the invention comprise a nonpolar solvent and at 0 least one compound selected from the group polyol, polyamine and amino alcohols.
The nonpolar solvents are selected from the same group which has already been described above
for the dispersions; preferably, the same nonpolar solvent is used for the dispersions and the
5 emulsions.
Polyols which are used in the process according to the invention are for example those as have
already been described above, it being preferred to use mixtures of polyols which, besides diols,
i.e. compounds which cany two hydroxy groups on each sp3-hybridized carbon atom, contain at
least 5 mol% of polyols which carry at least three hydroxy groups on each sp3-hybridized carbon
10 atom.
Polyamines that are used in the process according to the invention are for example those as have
already been described above.
Preferably, the nonpolar solvent for the dispersion and emulsion or the polyamine(s) is selected
such that the polyamine(s) islare insoluble or only slightly soluble, i.e. up to a maximum of 2% by
15 weight, preferably to a maximum of 0.5% by weight, in the nonpolar solvent.
Preferably, in step a), the dispersions are admixed with the emulsions in the presence of at least
one surfactant, or particularly preferably the emulsions comprise at least one surfactant.
Surfactants are for example anionic, cationic or amphoteric surfactants.
Anionic surfactants are for example alkyl sulphates, alkyl ether sulphates, alkylarylsulphonates,
20 alkyl succinates, alkyl sulphosuccinates, N-alkoylsarcosinates, acyltaurates, acylisethionates,
alkylphosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefinsulphonates, in
particular the alkali metal and alkaline earth metal salts, e.g. sodium, potassium, magnesium,
calcium, and also ammonium and triethanolamine salts.
Amphoteric surfactants are for example alkylaryl polyglycol ethers, such as polyoxyethylene
25 octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol or tributylphenyl
polyglycol ether, tris-steryl phenyl ether ethoxylates, alkylaryl polyether alcohols, isotridecyl
alcohol, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty acid esters such as e.g.
ethoxylated castor oil, polyoxyethylenealkylethers or polyoqxopylene, lauryl alcohol polyglycol
ether acetate, sorbitol esters or block copolymers based on ethylene oxide and/or propylene oxide.
30 According to step b), the mixtures obtainable according to step a) and the mixture resulting
according to step a) are reacted in the presence of catalyst with at least one polyisocyanate.
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Catalysts which can be used are in principle all catalysts which increase the rate of the reaction of
isocyanates with alcohols or amines. Catalysts which can be used here are all customary
urethanization catalysts of the organotin type, such as, for example, dibutyltin dilaurate, dibutyltin
diacetate, dibutyltin dialkyl maleates, tin stearate and tin octylate.
Furthermore, catalysts which can be used are tertiary amines, such as, for example,
triethylenediamine, 2-methyltriethylenediamine, N,N-dimethylaminoethylmorpholine, 1 -isobutyl-
2-methylimidazole, 1,8-diazabicyclo[5,4,O]undecene-7 and 1 ,5-diazabicyclo[4,3 41-nokne-5; and
catalysts of the metal salt type from organic acid, such as cobalt naphthenate, tetra(2-
10 ethylhexyl)titanate, iron(lII) 2-ethylhexoate, cobalt 2-ethylhexoate and zinc naphthenate.
Polyisocyanates which can be used in the process according to the invention are for example those
as have already been described above.
The polyisocyanates can be added in step b) either in the form of a solution or without dilution. If
they are added in the form of a solution, preference is given to using the nonpolar solvents already
15 used for the dispersions and/or emulsions. The temperature can be varied within a relatively wide
range and depends on the reactivity of the polyisocyanates, polyols, polyamines and amino
alcohols. In general, the reaction is carried out at a temperature from 10 to 70°C, preferably at 20
to 60°C.
In order to modify the properties of the products, further encapsulation layers can optionally also
20 be applied in an analogous way.
The suspensions obtainable according to the invention have a surprisingly high sedimentation
stability and storage stability.
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Tvitrogen-containing inorganic carrier materials
The compositions according to the invention further comprise at least one nitrogen-containing
inorganic carrier material, preferably inorganic carrier material containing one, two or three,
particularly preferably one, nitrogen.
5 Within the context of the invention, nitrogen-containing inorganic carrier materials are to be
understood as meaning inorganic carrier materials which have either been modified by adsorption
of at least one nitrogen-containing compound or by covalent bonding of a nitrogen-containing
compound, or which have been modified by adsorption of at least one nitrogen-containing
compound and by covalent bonding of a nitrogen-containing compound.
10 In a preferred embodiment, the nitrogen-containing, inorganic carrier materials contain the
nitrogen in organically bonded form, where, within the context of the invention, organically
bonded nitrogen is to be understood as meaning nitrogen which has at least one bond to a carbon
atom, with the exception of cyanide and isocyanate ions and hydrocyanic acid and isocyanic acid.
The nitrogen-containing inorganic carrier materials according to the invention are preferably solid
15 at room temperature.
The nitrogen-containing inorganic carrier materials according to the invention are preferably
prepared by reacting inorganic carrier materials with at least one nitrogen-containing compound,
the nitrogen-containing compounds preferably being organic compounds.
In a preferred embodiment, nitrogen-containing inorganic carrier materials according to the
20 invention have a nitrogen content of 0.05 to 10% by weight, preferably 0.1 to 10% by weight.
Unless stated otherwise, nitrogen contents were and are determined quantitatively by elemental
analysis by means of a combustion method.
Since the reaction mechanisms in the case of the reaction of nitrogen-containing compounds with
the inorganic carrier materials, especially in those cases where covalent bonds are also formed, are
25 often unclear and complex and cannot be fully explained as regards structure, the term nitrogencontaining
inorganic carrier materials also includes those which have been obtained by reacting
inorganic carrier materials with nitrogen-containing compounds, the ranges specified generally and
preferably being applicable in the same way to nitrogen-containing inorganic carrier materials.
Suitable inorganic carrier materials are for example and preferably silicas such as for example
30 precipitated silicas, such as silica gels, mesoporous silicates, xerogels, aerogels, fumed silicas,
silicas modified with inorganic, organic or organometallic radicals, for example silicas modified
with dichlorodialkylsilanes, kieselguhr, porosils for example zeosils, clathrasils or dealuminated
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zel))'es, aluminosilicates, zeolites, natural or synthetic tectosilicates, natural silicates such as for
example vermiculite, mica or fumed metal oxides for example titanium dioxides, for example in
anatase or rutile modification, including fumed metal mixed oxides.
Preference is given to fumed silicas, in particular hydrophilic or hydrophobic ones, for example
5 those commerciaIly available under the name ~ e r o s iflr~om Evonik-Degussa, with the product
~ e r o s i2l0~0 being particularly preferred.
It is also preferred that the inorganic carrier material contains no organoborane if the heterocyclic
3-ring compound is an aziridine.
Preference is likewise given to hydrophilic or hydrophobic precipitated silicas, in particular
10 hydrophilic or hydrophobic ones, for example those commercially available under the name
sipernat@ from Evonik-Degussa. Here, the products sipernatB22s and sipernat@'50s are
particularly preferred.
The nitrogen-containing inorganic carrier materials present in the compositions according to the
invention preferably have a particle size of 0.001 to 1000 pm, in particular 0.005 to 500 pm.
15 Preferably, the nitrogen-containing inorganic carrier materials are characterized by the ability to
absorb liquids, measured by their DBP absorption capacity (DBP = dibutyl phthalat5 see
DIN 53601 or IS0 4656) in grams per 100 g of carrier material. Preferably, the DBP absorption
capacity of the carrier materials according to the invention is 0.1 to 800 g/100 g, particularly
preferably 1 to 500 dl00 g of carrier material.
20 The nitrogen-containing inorganic carrier materials present in' the compositions according to the
invention preferably have a specific surface area [m21g], determined in accordance with the
Bninauer, Emmett and Teller method (BET surface area; J.Arn.Chem.Soc. 60, 309 (1938)) in
accordance with IS0 579411 (Annex D) of 1 to 1200 m21g, particularly preferably 50 to 900 m21g.
Suitable nitrogen-containing compounds are for example those in which the nitrogen is organically
25 bonded.
. Such compounds include for example mononitrogen compounds and polynitrogen compounds:
Mononitrogen compounds are for example those of the formula (II)
3 0
R2R3 R ~ N (a)
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R2, R3 and R~ in each case independently of one another are hydrogen, alkyl, alkenyl or
aryl or painvise together form a 3 to 7 membered N-heterocyclic, aliphatic,
unsaturated or aromatic ring
where the radicals alkyl, alkenyl or aryl or the 3 to 7 membered
N-heterocyclic, aliphatic, unsaturated or aromatic ring are either
unsubstituted or mono- or polysubstituted by radicals which are selected
from the group hydroxyl, fluorine, chlorine, bromine, iodine, carboxyl,
alkylsulphonyl, arylsulphonyl, nitrile or isonitrile,
10 but where at least one of the radicals R2, R3 and R4 is not hydrogen.
Compounds of the formula ( are for example aminoethanol and (2-[(l-methylpropyl)
amino]ethanol.
15 Polynitrogen compounds are for example polyamines such as for example
aliphatic diamines such as for example ethylenediamine, 1,2- and 1,3-propanediamine,
2-methyl- l,2-propanediamine, 2,2-dimethyl- 1,3-propanediamine, 1,3- and 1,4-
butanediamine, 1,3- and 1,5-pentanediamine, 1,6-hexanediamine, 2,2,4- and 2,4,4-
trimethylhexamethylenediamine and mixtures thereof, 1,7-heptanediamine, 1,8-
octanediamine, 1,9-nonanediamine, 1, 1 0-decanediamine, 1,ll -undecanediamine, 1,12-
dodecanediamine, methylbis(3-aminopropyl)amine, 1,5-diamino-2-methylpentane
(Ml'MD), 1,3-diaminopentane (DAMP), 2,5-dimethyl- l,6-hexarnethylenediamine,
cycloaliphatic polyamines such as for example 1,3- and 1,4-diaminocyclohexane, bis(4-
aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3-
ethylcyclohexyl)methane, 2-methylpentamethylenediamine, bis(4-amino-3,s-dimethylcyclohexyl)
methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= isophoronediamine
or IPDA), 2- and 4-methyl-1,3-diaminocyclohexdnea nd mixtures thereof, 1,3- and
1,4-bis(aminomethyl)cyclohexane, 1 -cyclohexylamino-3-aminopropane, 2,5(2,6)-
bis(aminomethyl)bicyclo[2.2.l]heptane (NBDA, produced by Mitsui Chemicals),
3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1 .~~.~]decane, 1,4-diamino-2,2,6-trimethylcyclohexane
(TMCDA), 3,9-bis(3 -aminopropyl)-2,4,8,1 O-tetraoxaspiro[5 .5]undecane,
piperazine, 1 -(2-aminoethyl)piperazine,
aromatic polyamines such as 1,3- and 1,4-xylylenediamine;
di- or polyvalent aliphatic mines which, besides one or more primary amino groups, carry
more than one secondary amino group, such as diethylenetriamine (DETA),
triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine and
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-15-
e higher
homologues of linear polyethyleneamines, N,Nt-bis(3 -
aminopropyl)ethylenediamine, polyvinylamines, and also polyethyleneirnines of varying
degree of polymerization (molar mass range 500 to 1 000 000 glmol), as are available for
example under the trade name ~ u ~ a s oflro@m BASF- +i n pure form or as aqueous solutions,
these polyethyleneimines also containing tertiary amino groups besides primary and
secondary amino groups;
polyamidoarnines
ether-group-containing aliphatic polyamines such as bis(2-aminoethyl)ether, 4,7-
dioxadecane- 1 , 1 0-diamine, 4,9-dioxadodecane- 1 J2-diamine and higher oligomers thereof,
polyoxyalkylene polyamines with two or three amino groups, for example available under
the name JeffamineB (from Huntsman Chemicals), under the name'~o1~etheramin(fer om
BASF) or under the name PC mine@ (from Nitroil), as well as mixtures of the
aforementioned polyamines.
15 Particularly suitable nitrogen-containing compounds which may be mentioned are aziridines.
Suitable aziridines are those which contain one or more aziridine groups.
Preferred aziridines are for example aziridine compounds of the formula (III)
where
20 R5 is hydrogen, alkyl or cycloalkyl, which are in each case unsubstituted or substituted and/or
mono- or polyethylenically unsaturated, in each case substituted or unsubstituted
fullerenyl, aryl, alkoxy, alkoxycarbonyl, arylcarbonyl, alkanoyl, carbamoyl or
oxomethylene,
R6, R7, R* and R9 independently of one another have the same meaning as R5 and additionally
25 independently are halogen, hydroxyl, carboxyl, alkylsulphonyl, arylsulphonyl, nitrile,
isonitrile, or the radicals
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- 16-
R6 ' d R8 or R7 I and R ~t,o gether with the carbon atoms to which they are bonded, form a 5- to 10-
membered carbocyclic ring which is not further substituted or further substituted and/or
mono- or polyethylenically unsaturated.
Suitable monofunctional aziridines of the formula (m) are for example those in which R6 and R' or
5 R7 and R9, together with the carbon atoms to which they are bonded, form a 5- to 10-membered
carbocyclic ring which is not further substituted or further substituted and/or mono- or
polyethylenically unsaturated.
In particular, these are those of the formula (IV)
10 where the carbocyclic ring is unsubstituted or is further substituted with one or more substituents
selected from the series halogen, hydroxyl, 0x0, carboxyl, alkylsulphony, arylsulphonyl, nitrile,
isonitrile, allcyl or cycloalkyl, which are in each case unsubstituted or substituted andor mono- or
polyethylenically unsaturated, or substituted or unsubstituted fullerenyl, aryl, alkoxy,
alkoxycarbonyl or alkanoyl, and
15 n is a number from 0 to 6, preferably 0 or 1.
Preference is likewise given to those monofunctional aziridine compounds of the formula (m) in
which R5 is a radical of the formula
in which
R'' is -H or alkyl, preferably -H, -CH3, -C2H5, particularly preferably -CH3, -C2HS,
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- 17-
g Qnumber fiom 1 to 4, preferably 1 to 3, particularly preferably 1 or 2,
h is a number fiom 1 to 11, preferably 1 to 5 and particularly preferably 1 to 3
and the other radicals have the above meaning.
In particular, preference is given to those compounds of the formula (ID) which correspond to the
5 compound of the formula (V) or (VI),
where
10 R" is -H or alkyl, preferably -H or -CH3, particularly preferably -CH3,
R12 is -H or allcyl, preferably -H or -CH3, particularly preferably -CH3 and the other radicals
have the above meaning.
Particular preference is given to aziridines which have two or more aziridine functions. By way of
example, compounds of the formula (VII) are to be mentioned,
15
in which
A is an m-valent aliphatic, cycloaliphatic or aromatic radical, which is optionally substituted,
m is a number from 2 to 5, in particular 2 or 3, and
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- 18-
R I ~for each m unit is in each case independently hydrogen or Cl-C4-alkyl, in particular CHI or
CH2CH3.
If m = 2, A is preferably C2-Clo-alkylene,
in particular
is a phenylene, in particular the bivalent radical of the formula
If m = 3, A is preferably the trivalent radical of the formula
Preference is given to those compounds of the formula (V) which correspond to the formulae
wm> - (XI>
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Likewise preferred polyfunctional aziridine compounds are Michael addition products of
optionally substituted ethyleneimine onto esters of polyhydric alcohols with a#-unsaturated
5 carboxylic acids and. the addition products of optionally substituted ethyleneimine onto
polyisocyanates.
Suitable alcohol components are for example trimethylolpropane, neopentyl glycol, glycerol,
pentaerythritol, 4,4'-isopropylidenediphenol, 4,4'-methylenediphenol and polyvinyl alcohols.
Suitable a,P-unsaturated carboxylic acids are for example acrylic acid and methacrylic acid,
10 crotonic acid and cinnamic acid. Particular preference is given to acrylic acid. The corresponding
polyhydric alcohols of the a$-unsaturated carboxylic acid esters can optionally be alcohols which
have been extended, one or more times, on their OH functions, in some cases completely, with
alkylene oxides" These may be for example the aforementioned alcohols extended one or more
times with allcylene oxides. In this respect, reference is also made to US 4,605,698, the disclosure
15 of which is incorporated into the present invention by reference. Alkylene oxides that are
particularly suitable according to the invention are ethylene oxide and propylene oxide.
Examples of polyisocyanates suitable for the reaction with optionally substituted ethyleneimine are
those specified on page 4, lines 33 - 35 of W02004/050617 A.
Examples of aziridines suitable according to the invention are those specified on page 3, lines
20 29 - 34 of W02004/050617 A.
Preference is likewise given to those aziridines as are described for example in US 3,225,013
(Fram), US 4,490,505 (Pendergrass) and US 5,534,39 1 (Wang).
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-20-
Pr rence is likewise given to those aziridines of the formula (III) which have at e least three
aziridine groups, such as, for example, trimethylolpropane tris[3-(l-aziridinyl)propionate],
trimethylolpropane tris[3-(2-methyl-l-aziridinyl)propionate], trimethylolpropane tris[2-
aziridinylbutyrate], tris(1-aziridiny1)phosphine oxide, tris(2-methyl-l-aziridiny1)phosphine oxide,
5 pentaerythritol tris[3-(1-aziridiny1)propionatel and pentaerythritol tetrakis[3-(laziridiny1)
propionatel.
Of these, preference is given particularly to trirnethylolpropane tris[3-(l-aziridinyl)propionate],
trimethylolpropane tris[3-(2-methyl-l-aziridinyl)propionate], trimethylolpropane tris[2-
aziridinylbutyrate], pentaerythritol tris[3-(l-aziridiny1)propionatel and pentaerythritol tetrakis[3-
1 0 (1 -aziridinyl)propionate] .
Trimethylolpropane tris[3 -(1 -aziridinyl)propionate], trimethylolpropane tris[3 -(2-methyl- 1 -
aziridiny1)propionatel and pentaerythritol tetrakis[3-(l-aziridinyl)propionate] are particularly
preferred.
Preference is likewise given to polyfunctional aziridines of the formula (XII)
in which
B is the radical of an aliphatic polyol which has at least x OH functions, where x OH
functions are substituted by the radical of the above brackets,
f is a number from 0 to 6, in particular from 1 to 3,
20 x is a number greater than or equal to 2, in particular 2 to 500 000 and
R'~R, 15, R16 and R17, in each case independently of one another, have the identical meaning to the
radicals R~ to R9 in the formula (II).
Particular preference is given to those aziridines of the formula (VI) in which x is 3 or 4 and B is a
3- or 4-fold OH-functional polyol.
PO0 1 00530-Foreign Countries . . .- - .-, . - 21 -
P w l a r preference is given to aziridines of the formula (XD) which correspond to the formulae
(m>- ( XV)
in which
RI4 is hydrogen or CH3.
Particular preference is given to the aziridine compound of the formula ma), where R ' ~= methyl,
also known as Crosslinker CX-100 from DSM, and the hardener product "Corial Harter AN" from
10 BASF, which comprises the aziridine of the formula (VIa) where R14 = hydrogen.
A preferred "alkyl" here is a linear or branched alkyl radical having 1 to 20, preferably 1 to 12,
carbon atoms. Examples of alkyl radicals according to the invention are methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octyl etc. The
aforementioned alkyl radicals can either be unsubstituted or mono- or polysubstituted by the
15 following radicals: alkoxy, preferably C1-C12-alkoxy, nitro, monoalkylamino, preferably CI-Clr
monoalkylamino, dialkylamino, preferably di[C1-C12-Ialkylamino, cyano, halo, haloakyl,
preferably trifluoromethyl, alkanoyl, aminocarbonyl, monoalkylaminocarbonyl,
dialkylaminocarbonyl, alkylamido, preferably C1-C12-alkylamido, alkoxycarbonyl, preferably C1-
C12- alkoxycarbonyl, alkylcarbonyloxy, preferably C1-C12-alkylcarbonyloxy,ar yl, preferably
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- 22 -
p w l or aryl substituted by halogen, CI-C12-alkyl or CI-Cli-alkoxy, heterocyclic 3-ring groups, in
particular aziridine or epoxy groups, or substituents such as those mentioned above which contain
these groups.
The nitrogen-containing inorganic carrier materials according to the invention can moreover
5 comprise further compounds, for example solvents such as for example esters of mono- or
polybasic carboxylic acids (e.g. mixtures comprising diisobutyl adipate, diisobutyl glutarate,
diisobutyl succinate), preferably VOC-free or low-VOC solvents, where VOC (volatile organic
compounds) are understood as meaning volatile organic compounds with a boiling point of less
than 250°C, emulsifiers such as for example castor oil ethoxylates, dispersion auxiliaries such as,
10 for example, polyvinyl alcohols, chelating reagents as specified for example in WO 98122543 A,
one or more stabilizers from the series of antioxidants, free-radical scavengers, UV stabilizers
and/or UV absorbers (for examples see below). In many cases, synergistic effects are observed
here. The reaction of the inorganic carrier material can for these compounds too preferably take
place analogously to processes a) - d) (see below).
15 During the preparation of the nitrogen-containing inorganic carrier materials, the following are for
example used:
0.001 to 80% by weight, preferably 0.005 to 60% by weight, in particular 0.01 to 50% by
weight, of at least one nitrogen-containing compound and
1
20 - 99.999% by weight, preferably 40 - 99.995% by weight, particularly preferably 50 -
99.99% by weight, of at least one inorganic carrier material.
As preferred further constituents, the nitrogen-containing inorganic carrier materials comprise
0.0d01 to 8% by weight, preferably 0.0005 to 6% by weight, in particular 0.001 to 5% by weight,
of emulsifiers. Moreover, the nitrogen-containing inorganic carrier materials according to the
invention can comprise 0.1 to 15% by weight, preferably 0.5 to 10% by weight, in particular 1 to
25 6% by weight, of a solvent.
The nitrogen-containing inorganic carrier materials can be produced for example by
a) mixing at least one nitrogen-containing compound, preferably one liquid nitrogen-containing
compound or solutions of at least one preferably liquid, nitrogen-containing compound in an
organic solvent, preferably in a VOC-free or low-VOC solvent, with an inorganic carrier, or
30 b) dissolving at least one nitrogen-containing compound in an organic solvent and mixing it with
an inorganic carrier material, optionally with the addition of suitable dispersion auxiliaries,
and isolating the nitrogen-containing inorganic carrier material, or
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- 23 -
c) w i n g an emulsion comprising at least one nitrogen-containing compound, water, at least one
organic solvent and optionally emulsifiers with an inorganic carrier material and isolating the
nitrogen-containing inorganic carrier material, or
d) mixing an aqueous dispersion of an inorganic carrier material comprising optionally dispersion
5 auxiliaries with an emulsion comprising at least one nitrogen-containing compound, water, at
least one organic solvent and optionally emulsifiers, and isolating the nitrogen-containing
inorganic carrier material,
e) mixing an aqueous dispersion of an inorganic carrier material comprising optionally dispersion
auxiliaries with an aqueous solution comprising at least one nitrogen-containing compound
10 and optionally emulsifiers, and isolating the nitrogen-containing inorganic carrier material,
where the isolation of the nitrogen-containing inorganic carrier material obtained according to
steps b) to e) preferably takes place by completely or partly separating off the solvent, in particular
by
filtration and optionally subsequent drying or
15 evaporation of the solvent, for example by fluidized-bed drying, spray-drying or rotary
evaporation, optionally under reduced pressure.
Process alternative a) preferably involves heterocyclic 3-ring compounds that are liquid under
standard conditions, with pasty compositions or dry powders in particular being formed.
In process alternative b), nonionogenic and anionic emulsifiers are suitable as preferred
20 dispersants.
Particular preference is given to carrier materials obtainable by the aforementioned process, in
particular by mode b), which comprise a surfactant, preferably anionic, cationic or amphoteric
surfactants.
(
Anionic surfactants are, for example, alkyl sulphates, alkyl ether sulphates, alkylaryl sulphonates,
25 alkylsuccinates, alkylsulphosuccinates, N-alkoylsarcosinates, acyltaurates, acylisethionates,
alkylphosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefinsulphonates, in
particular the alkali metal and alkaline earth metal salts, e.g. sodium, potassium, magnesium,
calcium and ammonium and triethanolamine salts.
Amphoteric surfactants are for example alkylaryl polyglycol ethers, such as polyoxyethylene
30 octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol or tributylphenyl
PO0 1 00530-Foreign Countries
-24-
p91ycol ether, trissteryl phenyl ether ethoxylates, alkylaryl polyether alcohols, isotridecyl
alcohol, polyoxyethylene fatty alcohol ethers, polyoxyethylene f&y acid esters such as e.g.
ethoxylated castor oil, polyoxyethyleneallcyl ethers or polyoxypropylene, lauryl alcohol polyglycol
ether acetate, sorbitol esters or block copolymers based on ethylene oxide and/or propylene oxide.
5 For mode c), preferred organic solvents for the oil-water emulsion that are used are preferably
those mentioned above.
Preferably, the preparation is in accordance with process alternative d). In particular, firstly a
dispersion of the inorganic carrier material in water is prepared here with the application of
preferably low shear energy, for example by using a paddle stirrer.
10 Further additives can be added in all modes in solid, liquid or in dissolved, dispersed or emulsified
form.
The aforementioned process alternatives preferably take place at a temperature of 0 to 35OC, in
particular at room temperature (20°C).
The nonpolar solvents
15 The nonpolar solvents preferably present in the compositions according to the invention are
organic solvents with a dielectric constant of less than 5.00 at 25OC, preferably hydrocarbons such
as, for example, aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, benzine
fractions, benzene, toluene, xylene, various petroleum ethers, hexane, cyclohexane, mineral oils,
paraffin oils, such as e.g. isoparaffms, highly aromatic petroleum such as naphtha, but also other
20 petroleum fractions or mixtures of the aforementioned solvents.
Composition .
The compositions according to the invention comprise for example
0.01 to 70% by weight, preferably 0.05 to 60% by weight, particularly preferably 0.1 to
50% by weight, of microcapsules comprising at least one iodine-containing biocide,
25 0.001 to 80% by weight, preferably 0.005 to 60% by weight, particularly preferably 0.01 to
50% by weight, of nitrogen-containing'inorganic carrier materials
such that the sum of microcapsules comprising at least one iodine-containing biocide and nitrogencontaining
inorganic carrier materials in the compositions according to the invention is 0.01 1 to
80% by weight, preferably 0.05 to 60% by weight and particularly preferably 5 to 50% by weight.
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- 25 -
If @ compositions according to the invention also comprise nonpolar solvent, the sum of
microcapsules comprising at least one iodine-containing biocide and nitrogen-containing inorganic
carrier materials and nonpolar solvent in the compositions according to the invention is preferably
90% by weight or more, preferably 95% by weight or more.
5 In a further embodiment, the weight ratio of nitrogen-containing inorganic carrier materials to the
iodine-containing biocides present in the microcapsules in the compositions according to the
invention is 1 : 100 to 2.8: 1, preferably 1 :50 to 2.25: 1 and particularly preferably 20: 1 to 1.8: 1.
In a further embodiment, the nitrogen-containing inorganic carrier materials and microcapsules
comprising at least one iodine-containing biocide are present in the compositions according to the
10 invention as a suspension in a nonpolar solvent.
Further constituents
Furthermore, the compositions according to the invention can comprise, as further ingredients,
adhesives such as carboxymethylcellulose, natural and synthetic pulverulent, granular or latex-like
polymers, such as gum Arabic, polyvinyl alcohol, polyvinyl acetate, and also natural
15 phospholipids, such as cephalins and lecithins, and synthetic phospholipids, as well as mineral and
vegetable oils.
Moreover, they can comprise dyes such as inorganic pigments, e.g. iron oxide, titanium oxide,
Prussian Blue and organic dyes, such as alizarin, azo and metallophthalocyanine dyes and trace
nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc, and also
20 stabilizers known for heterocyclic 3-ring compounds, in particular aziridine compounds, for
example tetramethylethylenediamine (TMEDA), triethylenediarnine and the 1,4-
diazabicyclo[2.2.2.]octane (DABCO) known from W02004/0506 17.
Furthermore, the compositions according to the invention can include skin preventers,
antioxidants, pigments and crystallization stabilizers as further ingredients.
25 The effectiveness and the action spectrum of the compositions according to the invention can be
increased if optionally further antirnicrobially effective compounds such as fungicides,
bactericides, herbicides, insecticides or other active ingredients for increasing the action spectrum
or achieving particular effects are added and/or co-used. Such compositions can then have an even
broader action spectrum.
30 In many cases, synergistic effects are observed here, i.e. the effectiveness of the mixture is greater
than the effectiveness of the individual components.
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-26-
Th@mmpositions according to the invention can therefore comprise one or more further biocides
which are selected from the following group:
triazoles such as:
azaconazole, azocyclotin, bitertanol, bromuconazole, cyproconazole, diclobutrazole,
5 difenoconazole, diniconazole, epoxyconazole, etaconazole, fenbuconazole, fenchlorazole,
fenethanil, fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole, imibenconazole,
ipconazole, isozofos, myclobutanil, metconazole, paclobutrazole, penconazole, propioconazole,
prothioconazole, simeconazole, (?)-cis- 1 -(4-chloropheny1)-2-(1H- 1,2,4-triazol- 1 -yl)cycloheptanol,
2-(l-tert-butyl)-l-(2-chlorophenyl)-3-(l,2,4-triazol-l-yl)propan-2-01, tebuconazole, tetraconazole,
10 triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal
salts and acid adducts;
imidazoles such as:
clotrimazole, bifonazole, climbazole, econazole, fenapamil, imazalil, isoconazole, ketoconazole,
lombazole, miconazole, pefurazoate, prochloraz, triflumizole, thiazolcar, 1-imidazolyl-1-(4'-chloro-
15 phenoxy)-3,3-dimethylbutan-2-one, and their metal salts and acid adducts;
pyridines and pyrimidines such as:
ancymidol, buthiobate, fenarimol, mepanipyrin, nuarimol, pyrolojfur, triamirol;
succinate dehydrogenase inhibitors such as:
benodanil, carboxim, carboxim sulphoxide, cyclafluramid, fenfuram, flutanil, furcarbanil,
20 furmecyclox, mebenil, mepronil, methfiroxam, metsulphovax, nicobifen, pyracarbolid,
oxycarboxin, Shirlan, Seedvax;
naphthalene derivatives such as:
terbinafine, naftifine, butenafme, 3-chloro-7-(2-aza-2,7,7-trimethyloct-3-en-5-yne);
sulphenamides such as:
25 dichlofluanid, tolylfluanid, folpet, fluorofolpet; captan, captofol;
benzimidazoles such as:
carbendazim, benomyl, fuberidazole, thiabendazole or their salts;
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m g o l i n e derivatives such as:
aldimorph, dimethomorph, dodemorph, falimorph, fenpropidin, fenpropimorph, tridemorph,
trimorphamid and their arylsulphonate salts such as, for example, p-toluenesulphonic acid and
p-dodecylphenylsulphonic acid;
benzothiazoles such as:
benzothiophene dioxides such as:
benzamides such as:
2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide, tecloftalam;
boron compounds such as:
boric acid, boric esters, borax;
formaldehyde and formaldehyde-releasing compounds such as:
benzyl alcohol mono(poly)hemiformal, 1,3-bis(hydroxymethyl)-5,5-dimethylimidazolidine-
2,4-dione (DMDMH), bisoxazolidine, n-butanol hemiformal, cis-1-(3-chloroally1)-3,5,7-triaza-
1 -azoniaadamantane chloride, 1- [1,3-bis(hydroxymethy1-2,5-dioxoimid~1-,3 -bis-
(hydroxymethyl)urea, dazomet, dimethylolurea, 4,4-dimethyloxazolidine, ethylene glycol
hemiformal, 7-ethylbicyclooxazolidine, hexahydro-S-triazine, hexamethylenetetramine,
N-hydrolrymethyl-N'-methylthiourea, methylenebismorpholine, sodium N-(hydroxymethy1)glycinate,
N-methylolchloroacetamide, oxazolidine, paraformaldehyde, taurolin, tetrahydro-
1,3-oxazine, N-(2-hydroxypropyl)aminemethanol, tetramethylolacetylenediurea (TMAD);
isothiazolinones such as:
N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-
3-one, 5-chloro-N-octylisothiazolinone, N-octylisothiazolin-3-one, 4,5-trimethyleneisothiazolinone,
4,5-benzoisothiazolinone;
aldehydes such as:
cinnamaldehyde, formaldehyde, glutaraldehyde, B-bromocinnamaldehyde, o-phthalaldehyde;
PO0 1 00530-Foreign Countries
t h p t e s such as:
thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate;
quaternary ammonium compounds and guanidines such as:
benzalkonium chloride, benzyldimethyltetradecylarnmonium chloride, benzyldimethyl-
5 dodecylammonium chloride, dichlorobenzyldimethylalkylammonium chloride, didecyldimethylammonium
chloride, dioctyldimethylammonium chloride, N-hexadecyltrimethylammonium
chloride, 1-hexadecylpyridinium chloride, irninoctadine tris(albesi1ate);
phenols such as:
tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol,
10 dichlorophene, 2-benzyl-4-chlorophenol, triclosan, diclosan, hexachlorophene, methyl p-hydroxybenzoate,
ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, octyl
p-hydroxybenzoate, o-phenylphenol, m-phenylphenol, p-phenylphenol, 4-(2-tert-butyl-
4-methylphenoxy)phenol, 4-(2-isopropyl-4-methylphenoxy)phenol, 4-(2,4-dimethy1phenoxy)-
phenol and their alkali metal salts and alkaline earth metal salts;
15 microbicides with an activated halogen group such as:
bronopol, bronidox, 2-bromo-2-nitro- 1,3-propanediol, 2-bromo-4'-hydroxyacetophenone, 1 -bromo-
3-chloro-4,4,5,5-tetramethyl-2-imidazolidinone B-bromo-B-nitrostyrene, chloracetamide,
chloramine T, 1,3-dibromo-4,4,5,5-tetramethyl-2-imidazolidinonde,ic hloramine T, 3,4-dichloro-
(3H)- 1,2-dithiol-3-one, 2,2-dibromo-3-nitrilepropionamide, 1,2-dibromo-2,4-dicyanobutane,
20 halane, halazone, mucochloric acid, phenyl 2-chlorocyanovinyl sulphone, phenyl 1,2-dichloro-
2-cyanovinyl sulphone, trichloroisocyanuric acid;
pyridines such as:
1-hydroxy-2-pyridinethione (and the Cu, Na, Fe, Mn, Zn salts thereof), tetrachloro-4-methylsulphonylpyridine,
pyrimethanol, mepanipyrim, dipyrithion, 1-hydroxy-4-methyl-6-(2,4,4-
PO0 1 00530-Foreign Countries
mwyacrylates or similar such as:
azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, ory, _s_ .a_s. trobin,
picoxystrobin, pyraclostrobin, trifloxystrobin, 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[[[l-[3-
(trifluoromethyl)phenyl]ethylidene] amino]oxy]methyl]phenyl]-3H- 1,2,4-triazol-3-one
5 (CAS NO. 185336-79-2);
metal soaps such as:
salts of the metals tin, copper and zinc with higher fatty acids, resin acids, naphthenic acids and
- phosphoric acid, such as, for example, tin naphthenate, tin octoate, tin 2-ethylhexanoate, tin oleate,
tin phosphate, tin benzoate, copper naphthenate, copper octoate, copper 2-ethylhexanoate, copper
10 oleate, copper phosphate, copper benzoate, zinc naphthenate, zinc octoate, zinc 2-ethylhexanoate,
zinc oleate, zinc phosphate, zinc benzoate;
metal salts such as:
salts of the metals tin, copper, zinc, and also chromates and dichromates, such as, for example,
copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper
15 sulphate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate;
oxides such as:
oxides of the metals tin, copper and zinc, such as, for example, tributyltin oxide, Cu20, CuO, ZnO;
oxidizing agents such as:
hydrogen peroxide, peracetic acid, potassium persulphate;
20 dithiocarbamates such as:
cufraneb, ferban, potassium N-hydroxymethyl-N'-methyldithiocarbamate, sodium dimethyldithiocarbamate,
potassium dimethyldithiocarbamate, mancozeb, maneb, metam, metiram, thiram,
zineb, ziram;
nitriles such as:
25 2,4,5,6-tetrachloroisophthalonitrile,d isodium cyanodithioimidocarbamate;
quinolines such as:
8-hydroxyquinoline and the copper salts thereof;
PO0 1 00530-Foreign Countries
- 30 -
o t v fungicides and bactericides such as:
bethoxazin, 5-hydroxy-2(5H)-furanone; 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone,
N-(2-p-chlorobenzoylethyl)hexaminium chloride, 2-0x0-2-(4-hydroxypheny1)acetohydroxycinnamoyl
chloride, tris-N-(cyclohexyldiazeniumdioxy)alurnini, N-(cyclohexyldiazenium-
5 dioxy)tributyltin or its potassium salts, bis-N-(cyclohexyldiazeniumdioxy) copper, iprovalicarb,
fenhexamide, spiroxamine, carpropamid, diflumetorin, quinoxyfen, famoxadone, polyoxorim,
acibenzolar S-methyl, furametpyr, thifluzamide, methalaxyl-M, benthiavalicarb, metrafenon,
cyflufenamid, tiadinil, tea tree oil, phenoxyethanol,
Ag, Zn or Cu-containing zeolites alone or incorporated into polymeric materials.
10 Very especially preferred are mixtures with
azaconazole, bromuconazole, cyproconazole, dichlobutrazol, diniconazole, diuron, hexaconazole,
metaconazole, penconazole, propiconazole, tebuconazole, dichlofluanid, tolylfluanid, fluorfolpet,
methfuroxam, carboxin, N-cyclohexyl-benzo[b]thiophenecarboxamide S,S-dioxide, fenpiclonil,
4-(2,2-difluoro- 1,3-benzodioxol-4-y1)- 1 H-pyrrole-3 -carbonitrile, butenafme, imazalil, N-methyl-
1 5 isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, dichloro-
N-octylisothiazolinone, mercaptobenzothiazole, thiocyanatomethylthiobenzothiazole,
thiabendazole, benzoisothiazolinone, N-(2-hydroxypropyl)aminomethanol, benzyl alcohol
(hemi)formal, N-methylolchloroacetamide, N-(2-hydroxypropyl)aminemethanol, glutaraldehyde,
omadine, Zn-omadine, dimethyl dicarbonate, 2-bromo-2-nitro- l,3-propanediol, bethoxazin,
20 o-phthalaldehyde, 2,2-dibromo-3-nitrilepropionamide, 1,2-dibromo-24-dicyanobutane, 1,3-
bis(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione (DMDMH), tetramethylolacetylenediurea
(TMAD), ethylene glycol hemiformal, p-hydroxybenzoic acid,
carbendazim, chlorophen, 3-methyl-4-chlorophenol, o-phenylphenol.
Apart from with the abovementioned fungicides and bactericides, mixtures with a good efficacy
25 are, moreover, also prepared with other active ingredients:
insecticides / acaricides / nematicides:
abamectin, acephate, acetamiprid, acetoprole, acrinathrin, alanycarb, aldicarb, aldoxycarb, aldrin,
allethrin, alpha-cypermethrin, amidoflumet, amitraz, avermectin, azadirachtin, azinphos A,
azinphos My azocyclotin,
30 Bacillus thuringiensis, barthrin, 4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-
1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin,
bioresmethrin, bioallethrin, bistrilfluron, bromophos A, bromophos My bufencarb, buprofezin,
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-31 -
b u ~ i o p h o sb,u tocarboxim, butoxycarboxim,
cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan, cartap, quinomethionate,
cloethocarb, chlordane, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron,
chlormephos, N-[(6-chloro-3-pyridinyl)methyl]-N'-cyano-N-methylethaneimidamide,c hlorpicrin,
chlorpyrifos A, chlorpyrifos M, cis-resmethrin, clocythrin, clothiazoben, cypophenothrin,
clofentezin, coumaphos, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,
cypermethrin, cyromazin,
decamethrin, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, dialiphos,
diazinon, 1,2-dibenzoyl- l(1,l -dimethyl)hydrazine, DNOC, dichlofenthion, dichlorvos, dicliphos,
dicrotophos, difethialone, diflubenzuron, dimethoate, 3,5-dimethylphenyl methylcarbamate,
dimethyl(pheny1)silyImethyl-3-phenoxybenzyl ether, dimethyl(4-ethoxypheny1)silylmethyl-3-
phenoxybenzyl ether, dimethylvinphos, dioxathion, disulphoton,
eflusilanate, emamectin, empenthrin, endosulphan, EPN, esfenvalerate, ethiofencarb, ethion,
ethofenprox, etrirnphos, etoxazole, etobenzanid,
fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb,
fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fensulphothion, fenthion, fenvalerate,
fipronil, flonicamid, fluacrypyrim, fluazuron, flucycloxuron, flucythrinate, flufenerim,
flufenoxuron, flupyrazofos, flufenzine, flumethrin, flufenprox, fluvalinate, fonophos,
formethanate, formothion, fosmethilan, fosthiazate, fubfenprox, furathiocarb,
halofenozide, HCH (CAS RN: 58-89-9), heptenophos, hexaflumuron, hexythiazox,
hydramethylnon, hydroprene,
imidacloprid, imiprothrin, indoxycarb, iprinomectin, iprobenfos, isazophos, isoamidophos,
isofenphos, isoprocarb, isoprothiolane, isoxathion, ivermectin,
kadedrin,
lambda-cyhalothrin, lufenuron,
malathion, mecarbam, mervinphos, mesulphenphos, metaldehyde, methacrifos, methamidophos,
methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxiectin,
naled, NI 125, nicotine, nitenpyram, noviflumuron,
omethoate, oxamyl, oxydemethon M, oxydeprofos,
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- 32 -
p-ion A, parathion M, penfluron, permethrin, 2-(4-phenoxyphenoxy)ethyl ethylcarbamate,
phenthoate, phorate, phosalon, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,
pirimiphos A, prallethrin, profenophos, promecarb, propaphos, propoxur, prothiophos, prothoate,
pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyridalyl,
5 pyrimidifen, pyriproxifen, pyrithiobac-sodium,
quinalphos,
resmethrin, rotenone,
salithion, sebufos, silafluofen, spinosad, spirodiclofen, spiromesifen, sulphotep, sulprofos,
tau-fluvalinate, taroils, tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin,
10 temephos, terbam, terbufos, tetrachlorvinphos, tetramethrin, tetramethacarb, thiacloprid, thiafenox,
thiamethoxam, thiapronil, thiodicarb, thiofanox, thiazophos, thiocyclam, thiomethon, thionazin,
thuringiensin, tralomethrin, transfluthrin, triarathen, triazophos, triazamate, triazuron, trichlorfon,
triflumuron, trimethacarb,
vamidothion, xylylcarb, zetamethrin;
fentin acetate, metaldehyde, methiocarb, niclosamide;
herbicides and algicides:
acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulphuron,
amitrole, ammonium sulphamate, anilofos, asulam, atrazine, azafenidin, aziptrotryne,
20 azimsulphuron,
benazolin, benfluralin, benfuresate, bensulphuron, bensulphide, bentazone, benzofencap,
benzthiazuron, bifenox, bispyribac, bispyribac-sodium, borax, bromacil, bromobutide,
bromofenoxim, bromoxynil, butachlor, butamifos, butralin, butylate, bialaphos, benzoyl-prop,
bromobutide, butroxydim,
25 carbetamide, carfentrazone-ethyl, carfenstrole, chlomethoxyfen, chloramben, chlorbromuron,
chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, chloransulam-methyl;
cinidon-ethyl, chlorotoluron, chloroxuron, chlorpropham, chlorsulphuron, chlorthal, chlorthiamid,
cinmethylin, cinosulphuron, clefoxydim, clethodim, clomazone, chlomeprop, clopyralid,
cyanamide, cyanazine, cycloate, cycloxydim, chloroxynil, clodinafop-propargyl, cumyluron,
30 clometoxyfen, cyhalofop, cyhalofop-butyl, clopyrasuluron, cyclosulphamuron,
PO0 1 00530-Foreign Countries
- 33 A
dic@ulam, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican,
diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethipin, dinitramine, dinoseb, dinoseb
- acetate, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diuron, DNOC, DSMA, 2,4-D,
daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicamba, dichlobenil,
5 dimethamid, dithiopyr, dimethametryn,
eglinazine, endothal, EPTC, esprocarb, ethalphluralin, ethidimuron, ethofimesate, ethobenzanid,
ethoxyfen, ethametsulphuron, ethoxysulphuron,
fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulphuron, fluazifop, fluazifop-P,
fuenachlor, fluchloralin, flufenacet, flumeturon, fluorocglycofen, fluoronitrofen, flupropanate,
10 flurenol, fluridone, flurochloridone, fluroxypyr, fomesafen, fosamine, fosametine, flampropisopropyl,
flamprop-isopropyl-L, flufenpyr, flumiclorac-pentyl, flumipropyn, flumioxzim,
flurtamone, flumioxzim, flupyrsulphuron-methyl, fluthiacet-methyl,
glyphosate, glufosinate-ammonium,
haloxyfop, hexazinone,
15 imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr, imazaquin, imazethapyr, ioxynil,
isopropalin, imazosulphuron, imazomox, isoxaflutole, imazapic,
ketospiradox,
lactofen, lenacil, linuron,
MCPA, MCPA-hydrazide, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet,
20 mefluidide, mesosulphuron, metam, metamifop, metamitron, metazachlor, methabenzthiazuron,
methazole, methoroptryne, methyldymron, methyl isothiocyanate, metobromuron, metoxuron,
metribuzin, metsulphuron, molinate, monalide, monolinuron, MSMA, metolachlor, metosulam,
metobenzuron,
naproanilide, napropamide, naptalam, neburon, nicosulphuron, norflurazon, sodium chlorate,
25 oxadiazon, oxyfluorfen, oxysulphuron, orbencarb, oryzalin, oxadiargyl,
propyzamide, prosulphocarb, pyrazolate, pyrazosulphuron, pyrazoxyfen, pyribenzoxim,
pyributicarb, pyridate, paraquat, pebulate, pendimethalin, pentachlorophenol, pentoxazone,
pentanochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulphuron,
prodiamine, profoxydim, prometryn, propachlor, propanil, propaquizafob, propazine, propham,
30 propisochlor, pyriminobac-methyl, pelargonic acid, pyrithiobac, pyraflufen-ethyl,
PO0 1 00530-Foreim Countries
- 34 -
qul)"erac, quinocloamine, quizalofop, quizalofop-P, quinchlorac,
rimsulphuron,
sethoxydim, sifuron, simazine, simetryn, sulphosulphuron, sulphometuron, sulphentrazone,
sulcotrione, sulphosate,
5 tar oils, TCA, TCA-sodium, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn,
thiazafluoron, thifensulphuron, thiobencarb, thiocarbazil, tralkoxydim, triallate, triasulphuron,
tribenuron, triclopyr, tridiphane, trietazine, trifluralin, tycor, thdiazimin, thiazopyr, triflusulphuron,
vernolate.
The compositions according to the invention can comprise the aforementioned further biocides
10 either likewise in microencapsulated form or unencapsulated form or both in encapsulated and in
unencapsulated form. If they are present at least partly in encapsulated form, the further biocides
can be present in the same microcapsules (co-encapsulation) or in separate microcapsules.
However, the compositions according to the invention can also in each case be free from
aforementioned further biocides in toto or in each case free from each of the individual
15 aforementioned compounds.
Effect
It has been found that the decomposition of iodine-containing biocides in the compositions
according to the invention, for example as a result of light or temperature influences, can be
effectively prevented.
20 Moreover, the compositions according to the invention themselves are storage-stable for a long
period.
Moreover, it has been found that the use of the compositions according to the invention in coating
compositions is not associated with any application-related disadvantages such as, for example, an
extension in drying time.
25 ' The compositions according to the invention are therefore suitable in particular for protecting
industrial materials. Industrial materials are, for example, adhesives, sizes, paper and cardboard, .
textiles, leather, wood, wood-based materials, coating compositions and plastic articles, cooling
lubricants and other materials which can be infested, altered or decomposed by microorganisms.
PO0 1 00530-Foreign Countries
- 35.-
Exgples of microorganisms which can bring about a decomposition or an alteration of the
industrial materials are bacteria, fungi, yeasts, algae and slime organisms. The active ingredients
according to the invention are preferably effective against fungi, in particular moulds, wooddiscolouring
and wood-destroying fungi (Basidiomycetes) and also against slime organisms and
bacteria.
Microorganims of the following genera may be mentioned by way of example:
Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as
Chaetomium globosum, Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus
tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pulldans, Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas,
such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus.
The invention therefore further provides industrial materials equipped with the compositions
according to the invention, and also the use of the compositions according to the invention for
protecting industrial materials against infestation, alteration or decomposition by microorganisms,
and also a method for protecting industrial materials against infestation, alteration or
decomposition by microorganisms by treating the industrial .materials with the compositions
according to the invention.
The compositions according to the invention are very particularly preferably suitable for equipping
coating compositions.
The invention therefore encompasses coating compositions comprising
at least one binder
microcapsules comprising at least one iodine-containing biocide
at least one nitrogen-containing inorganic carrier material
at least one nonpolar solvent.
Coating compositions can be for example paints, varnishes, stains, primers or impregnation
systems.
For the microcapsules comprising at least one iodine-containing biocide, the nitrogen-containing
inorganic carrier materials and the nonpolar solvents, the same ranges, preferred ranges,
preparation methods as have been described above for the compositions according to the invention
are applicable.
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-36 -
B ers are for example oxidatively drying binders such as oxidatively drying alkyd * resins or binders which form films by means of coalescents, such as in particular polymer latices.
As regards the definition of the term "alkyd resins", reference is made to the above disclosure,
which applies here in the same way.
5 The coating compositions according to the invention comprise preferably 1 to 80% by weight,
preferably 2 to 70% by weight and particularly preferably 3 to 60% by weight, of binder,
preferably alkyd resin.
Preferably, the coating compositions according to the invention, if they comprise oxidatively
drying binders, further comprise at least one transition metal siccative.
10 Transition metal siccatives are for example and preferably salts of transition metals of groups Vb,
VIb, VIB, VIIt and Ib of the chemical Periodic Table. In particular, they are the salts of cobalt,
manganese, vanadium, nickel, copper and iron, particularly preferably cobalt, manganese, iron and
vanadium. They do not necessarily have to be used alone, but can also be used in combination with
non-transition metal salts, such as for example lead, calcium or zirconium.
15 Particularly preferred transition metal salts are soluble in the nonpolar solvents to more than 10 dl.
Preferably, these are the salts of carboxylic acids which have good compatibility with the binders,
in particular the alkyd resins, and at the same time ensure sufficient solubility of the metal salt.
Preference is given to using transition metal salts of fatty acids, such as oleates or linoleates, of
resin acids, such as resinates, or salts of 2-ethylhexanoic acid (octoates). Preferred siccatives based
20 on transition metal compounds are cobalt octoate and cobalt naphthenate, e.g. OctasoligenB-cobalt
12 from Borchers.
Preferably, the coating compositions according to the invention comprise the transition metal
siccative in an amount of 0.001 to 1% by weight, preferably 0.005 to 0.5% by weight and very
particularly preferably 0.01 to 0.1% by weight, in each case based on the binder.
25 In a preferred embodiment, the coating compositions according to the invention further comprise a
polar organic solvent, preferably a polar aprotic solvent. Polar organic solvents are those with a
dielectric constant of 5.00 or more at 2S°C, aprotic solvents are those with a pKa value at 20°C,
based on an aqueous scale or calculated on an aqueous comparative scale, of 20 or more.
Polar protic organic solvents are, for example, dipropylene glycol monomethyl ether (e.g. Dowanol
30 DPM from Dow Chemical), polar aprotic organic solvents are for example dimethylformamide and
dimethyl sulphoxide, and also e.g. etherified glycols, oligoglycols and polyglycols, etherified
PO0 1 00530-Foreinn Countries
paQls and esterified polyols, esters of mono- and polybasic carboxylic acids, e.g. diisobutyl
adipate, diisobutyl maleate (e.g. Rhodiasolv DIB).
Particular preference is given to a coating composition comprising
1 to 80% by weight, preferably 2 to 70% by weight, particularly preferably 3 to 60% by
5 weight, of alkyd resin as binder
0.01 to 5% by weight, preferably 0.05 to 3% by weight, particularly preferably 0.1 to 2%
by weight, of iodine-containing biocide present in the form of microcapsules
0.001 to 7% by weight, preferably 0.005 to 5% by weight, particularly preferably 0.01 to
4% by weight, of nitrogen-containing inorganic carrier materials,
10 2 to 97% by weight of organic solvent, preferably including up to 10% by weight, in
particular 0.01 to 7.5% by weight, based on the coating composition, of polar aprotic
solvent, and
0.001 to 3% by weight of transition metal siccative,
and optionally
15 between 0 and 50% by weight of colour pigments,
where the sum of the aforementioned components in the coating composition is at most 100.00%
by weight.
The coating compositions according to the invention can optionally further also comprise fillers,
skin preventers, rheology additives such as, for example, anti-settling agents and thioxotropic
20 agents, further biocides such as fungicides, bactericides, anti-fouling agents and algicides, process
additives, plasticizers, UV absorbers, UV stabilizers and heat stabilizers, as well as corrosion
inhibitors, in customary amounts.
For the further biocides, the disclosure given above for the compositions according to the
invention is applicable entirely analogously.
25 Additionally, further stabilizers can also be added to the binder formulations, examples being the
chelating reagents specified in WO 98122543, or heterocyclic 3-ring compounds, in particular
those with a heteroatom other than nitrogen, such as, for example, the organic epoxides specified
in WO 00116628. In many cases, synergistic effects are observed here.
PO01 0053 0-Foreign Countries
-38-
v, in the context of the use according to the invention, it is also possible to further add one
or more compounds from the series of antioxidants, free-radical scavengers, UV stabilizers,
chelators and UV absorbers, which sometimes have synergistic effects.
By way of example, UV stabilizers which may be mentioned are:
sterically hindered phenols, such as
2,6-di-tert-butyl-4-methylphenol2,- tert-butyl-4,6-dimethylphenol, 2,6-di-cyclopentyl-4-methylphenol,
2-(a-methylcyclohexyl)-4,6-dimethylphenoly2,6-di-octadecyl-4-methylpheonro l
2,6-di-tert-butyl-4-methoxymethylphenodli,e thyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate,
2,4-dimethyl-6-(1-methylpentadecyl)phenol, 2-methyl-4,6-bis[(octylthio)methyl]phenol,
2,6-di-tert-butyl-4-methoxypheno2l,,5 -di-tert-butylhydroquinone,2 ,5-di-tert-amylhydroquinone,
2,6-diphenyl-4-octadecyloxyphenol2,, 2'-thiobis(6-tert-butyl-4-methylphenol),'2,2'-thiobis(
4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methy1enebis(4,6-di-tert-buty1pheno1) 2,2'-ethylidenebis(4,6-di-tert-butylphenol),
4,4'-methylenebis(2,6-di-tert-butylphenol) 4,4'-methylenebis(6-tert-butyl-2-rnethylphenol),
1,l -bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butaney1 ,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)
butane, 1,3,5-tri(3,5-di-tert-buty1-4-hydroxyben1)-2,46-imeth1beeneis ooctyl
3,5-di-tert-butyl-4-hydroxybenzylmercapt0acetate1,, 3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)
isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbeils)o cyanurate, 1,3,5-tris[(3,5-ditert-
butyl-4-hydroxyphenyl)propionyloxyethyl]i socyanurate, dioctadecyl3,5-di-tertbutyl-
4-hydroxybenzylphosphonate, calcium monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
N,N'-di(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexmethylenediminey
N,N1-di(3 ,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediaminey
N,N1-di(3, 5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine3y, 9-bis[ l ,1 - dimethyl-2-[(3-tertbutyl-
4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,1O-tetraoxaspiro[5.5]undecane,
bis[3,3-bis(4'-hydroxy-3'-tert-butylphenyl)butanoic acid] ethylene glycol ester, 2,6-bis[[3-(1,ldimethylethyl)-
2-hydroxy-5-methylphenyl]octahydro-4,7-methanol-H -indenyll-4-methylphenol
(= Wingstay L), 2,4-bis(n-octylthio)-6-(3,5-di-tert-butyl-4-hydroxyphenylmino)-s-tiney
N-(4-hydroxyphenyl)octadecaneamide, 2,4-di-tert-butylphenyl3',5'-di-tert-butyl-4'-hydroxybenzoate,
(benzoic acid, 3,5-bis(1,l-dimethylethy1)-4-hydroxy-,h exadecyl ester), 3-hydroxyphenyl
benzoate, 2,2'-methylenebis(6-tert-butyl-4-methylphenolm)o noacrylate, 2-(1,l -dimethylethyl)-
6-[I-[3-(1,l -dimethylethyl)-5-(l,l-dimethylpropyl)-2-hydroxyphenyl]ethyl]-4-(1 , 1-dimethylpropy1)
phenyl ester, esters of 13-(3,5-di-tert-butyl-4-hydroxypheny1)propionic acid with
monohydric or polyhydric alcohols such as, for example, with methanol, octadecanol,
1,6-hexanediol,n eopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol,
PO0 1 00530-Foreign Countries .
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peerythritol, trishydroxyethyl isocyanurate or dihydroxyethyloxalamide,
esters of B-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric
alcohols such as, for example, with methanol, octadecanol, 1,6-hexanediol,n eopentyl glycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, trishydroxyethyl
5 isocyanurate or dihydroxyethyloxalamide.
Hindered amines, such as
bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate,
bis(2,2,6,6-tetramethyl-4-piperidy1)decanedhte dimethyl succinate-1-(2-hydroxyethy1)-
4-hydroxy-2,2,6,6-tetramethylpiperidinec opolymer,p oly[[6-[(I, 1,3,3-tetramethylbuty1)aminol-
10 1,3,5-triazine-2,4-diy1][(2,2,6,6-tetramethy1-4-piperidy1)imino]hexamethy1ene[(2,2,6,6-tetramethy1-
4-piperidyl)imino]] (CAS No. 7 1878-19-8), 1,5,8,12-tetrakis[4,6-bis(n-butyl-n1-, 2,2,6,6-pentamethyl-
4-piperidy1amino)-1 ,3,5-triazin-2-1-1518- teaazadodecane( CAS No. 106990-43-6),
bis(l72,2,6,6-pentamethyl-4-piperidyl)decanedioate~b is(l,2,2,6,6-pentamethyl-4-piperidyl)
2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butyalonatdeeyc anedioic acid, bis(2,2,6,6-tetramethyl-
15 4-piperidinyl) ester, Chimasorb 2020 (CAS No. 192268-64-7), poly[[6-morpholino-l,3,5-triazine-
2,4-diyl][ (2,2,6,6-tetramethyl-4-piperidinyl)imino]-l,6-hexanediyl[(2,2,6,6-tetramethyl-4-
piperidinyl)imino]], poly[[6-(4-morpholiny1)- 1,3,5-triazine-2,4-diyl[](I ,2,2,6,6-pentamethyl-4-
piperidiny1)iminol- l,6-hexanediyl[( l ,2,2 (9CI), 3 -dodecyl-
1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione3~- dodecyl-1-(1,2,2,6,6-
20 pentamethylpiperidin-4-y1)pyrrolidine-2,5-dione,4 -octadecanoyloxy-2,2,6,6-tetramethylpiperidine,
poly[[6-(cyclohexylamino)-1 ,3,5-triazine-2,4-diy1][(2,2,6,6-tetrame1-4-piperidin1)ino]-1 ,6-
hexanediy1[(2,2,6,6-tetramethyl-4-piperidinyl)imino]], 1H74H,5H,8H-2,3aY4a,6,7a,8ahexaazacyclopenta[
deflfluorene-43-dione, hexahydro-2,6-bis(2,2,6,6-tetramethyl-4-piperidinyl)
(CAS No. 109423-00-9),N ,N'-bis(fomyl)-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-,l6 -
25 hexanediamine, N-(tetramethyl-4-piperidinyl)maleimide-C20-24-a-olecfo polymer (CAS No.
19923 7-39-3), tetrakis(l,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-
piperidinyl tridecyl 1,2,3,4-butanetetracarboxylate, (1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-
tetramethyl-4-piperidinyl tridecyl ester), (2,4,8,1O-tetraoxaspiro[5.5]undecane-3,9-diethanol,
30 P,P,P',P'-tetramethyl-p,o lymer with 1,2,3,4-butanetetracarboxylica cid) (CAS No. 115055-30-6),
2,2,4,4-tetramethyl-12- oxo-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan(e,7 -oxa-3,20-
diazadispiro[5.1.11.2]heneicosane-20-propanoic acid, 2,2,4,4-tetramethyl-12- 0x0-,t etradecyl
ester), (7-oxa-3,20-diazadispi~-0[5.1.11.2]heneicosan-12- one,2 ,2,4,4-tetramethyl-20-
(oxiranylmethy1)-), (propanamide, N-(2,2,6,6-tetramethyl-4-piperidinyl)-3-[(2,2,6,6-tetramethyl4-
35 piperidiny1)aminol-), (1,3-propanediamine,N ,NW'-1, 2-ethanediylbis-p,o lymer with 2,4,6-trichloroPO0
1 00530-Foreign Countries
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1,- triazine, reaction products with N-butyl-2,2,6,6-tetramethyl-4-piperidina(m)C AS No.
136504-96-6), l,l'-ethylenebis(3,3,5,5-tetramethyl-2-piperazinone), (piperazinone, 1, l', 1 "-[I ,3,5-
triazine-2,4,6-triyltris[(cyclohexylimino)-2,l-ethanediyl]]tris[3,3,5,5-tetramethyl-), (7-oxa-3,20-
diazadispiro[5.1.11.2]heneicosane-20-propanoic acid, 2,2,4,4-tetramethyl-12- oxo-,d odecyl ester),
5 1,l -bis(l ,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxhenyl)ethene(,2 -propenoic
acid, 2-methyl-,m ethyl ester, polymer with 2,2,6,6-tetramethyl-4-piperidinyl2-propenoate)( CAS
No. 154636-12-I), (propanamide, 2-methyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-[(2,2,6,6-
tetramethyl-4-piperidiny1)aminol-), (D-glucitol, 1,3 :2,4-bis-0-(2,2,6,6-tetramethyl-4-
piperidiny1idene)-) (CAS No. 99473-08-2), N,N'-bis(2,2,6,6-tetramethyl-4-
10 piperidinyl)isophthalamide, 4-hydroxy-2,2,6,6-tetramethylpiperidine,
1- allyl-4-hydroxy-2,2,6,- tetramethylpiperdine,1 - benzy1-4-hydroxy-2,2,6,6-tetramethy1piperidine,
1 -(4-tert-butyl-2-buteny1)-4-hydroxy-2- 4-stearoyloxy-
2,2,6,6-tetramethylpiperidine, l-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine,
4-methacryloyloxy-1, 2,2,6,6-pentamethylpiperidine,1 ,2,2,6,6-pentamethylpiperidin-4-yjl3 -(33-di-
15 tert-butyl-4-hydroxyphenyl)propionate, 1- benzyl-2,2,6,6-tetramethyl-4-piperidinm aleate,
(di-2,2,6,6-tetramethylpiperidin-4-yl)a dipate, (di-2,2,6,6-tetramethylpiperidin-4-yls) ebacate,
(di-1,2,3,3,6-tetramethyl-2,6-diethylpiperidin-4-y1s)e bacate,
(di-1-allyl-2,2,6,6-tetramethylpiperidin-4-yplh)t halate, 1-propargyl-4-P-cyanoethyloxy-
2,2,6,6-tetramethylpiperidine1,- acetyl-2,2,6,6-tetramethylpiperidin-4-yalc etate, trimellitic
20 acid tri(2,2,6,6-tetramethylpiperidin-4-yl) ester, 1 -acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine,
dibutyl-malonic acid di(1,2,2,6,6-pentamethylpiperidin-4-yl) ester,
butyl(3,5-di-tert-butyl-4-hydroxybenzy1)malonic acid di(l,2,2,6,6-pentamethylpiperidin-4-yl) ester,
dibenzylmalonic acid di(1,2,2,6,6-pentamethylpiperidin-4-yl) ester, dibenzylrnalonic acid
di(1,2,3,6-tetramethyl-2,6-diethylpiperidin-4-y1)e ster, hexane-11,6'-bis(4-carbamoyl-
25 oxy-1 - n-butyl-2,2,6,6-tetramethylpiperidine)t,o luene-2',4'-bis(4-carbamoyloxy- 1- n-propyl-
2,2,6,6-tetramethylpiperidine), dimethyl-bis(2,2,6,6-tetramethylpiperidk~hy)&me,
phenyl-tris(2,2,6,6-tetramethylpiperidine-4-oxy)silane, tris(1-propyl-2,2,6,6-tetramethylpiperidin-
4-yl) phosphite, tris(1 -propyl-2,2,6,6-tetramethylpiperidin-4-ylp)h osphate,
phenyl[bis(l,2,2,6,6-pentamethylpiperidin-4-yl)phosphonate~d i(l,2,2,6,6-pentamethylpiperidin-4-yl)
30 sebacate, N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-l ,6-diamine,
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene- 1,6-diacetamide,
l-acetyl-4-(N-cyclohexylacetamido)-2,2,6lpiperidiney 4-benzylamino-2,2,6,6-tetramethylpiperidine,
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyladipamide,
N,N'-bis(2,2,6,6-tetramethy1piperidin-4-y1)-N,N'-dicyc1ohexy1(2-hydro~ropy1ene),
35 N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamin4e-~( bis-2-hydroxyethy1)
amino- 1,2,2,6,6-pentamethylpiperidine,4 -(3-methyl-4-hydroxy-5-tert-butyl-bemido)-
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2,%6-tetramethylpiperidine, 4-methacrylamino-1,2,2,6,6-pentamethylpiperidine9,- aza-8,8,10,10-
tetramethyl-l,5-dioxaspiro[5S lundecane, 9-aza-8,8,10,O1- tetramethyl-3-ethyl-
1,5-dioxaspiro[5.5]undecane, 8-aza-2,7,7,8,9,9-hexamethyl-~,4-dioxaspiro[4.5]decane,
9-aza-3-hydroxymethyl-3-ethyl-8,8,9,110O ,- pentamethyl-l-5-dioxaspiro[5.5]undecane,
5 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10O,-1t etramethyl-1,5-dioxaspiro[5S lundecane,
2,2,6,6-tetramethylpiperidine-4-spiro-2~e)-5'-spiro-5'-(1",3 "-dioxane)-2"-spiro-
4"-(2"',2"',6"',6"'-tetramethylpiperide), 3-benzyl-l,3,8-triaza-7,7,9,9-tetramethyl-
spiro[4.5]decane-2,4-dione,3 -n-octyl-l,3,8-triaza-7,7,9,9-tetramethyl-spiro-
[4.5]decane-2,4-dione,3 -allyl-1 ,3,8-triaza-1,7,7,9,9-pentamethyl-spiro[4.5]decane-2,4-dione,
10 3-glycidyl-l,3,8-triaza-7,7,8,9,9-pentamethyl-spiro[4.5]decane-2,4-dione7
2-isopropyl-7,7,9,9-tetramethyl1-- oxa-3,8-diaza-4-oxyspiro[4.5]decane,
2-butyl-7,7,9,9-tetramethyl- 1 -oxa-3,8-diaza-4-oxyspiro[4.5]decane,
- 2-isopropyl-7,7,9,9-tetramethyl1-
2-butyl-7,7,9,9-tetramethyl- 1- oxa-4,s-diaza--3ox yspiro[4.5]decane,
15 bis[P-(2,2,6,6-tetramethylpiperidino)ethyl] sebacate, a-(2,2,6,6-tetramethy1piperidino)acetic acid
n-octyl ester, 1,4-bis(2,2,6,6-tetramethy1piperidino)-2-butene N-hydroxymethyl-Nt-2,2,6,6-tetramethylpiperidin-
4-ylurea, N-methoxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-ylureay
N-methoxymethyl-N~-n-dodecyl-N'-2,2,6,6-tetramethylpiperidin-4-ylur0e-a(,2 ,2,6,6-tetramethylpiperidin-
4-y1)-N-methoxymethylurethane.
20 Phosphites and phosphonates, such as
tris(nonylpheny1) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)
pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylpheny1)pentaeitol diphosphite,
2,2'-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, tetrakis(2,4-di-tertbutylphenyl)[
l, 1'-biphenyll-4,4'-diylbisphosphonite2,, 2'-ethylidenebis(4,6-di-tert-butylphenyl)
25 fluorophosphite, dioctadecyl pentaerythritol diphosphonite, 2-[[2,4,8,1O-tetrakis(1,l-dimethylethyl)
dibenzo[d,fl [1,3,2]dioxaphosphin-6-1]ox]-N,N-bis[2-[[2,4,8,10-tetrakis(1,-1d imethylethyl)
dibenzo[d,fl [1,3,2]dioxaphosphin-6-yl]oxy]ethyl]ethanamine (CAS No. 804 10-33-9),
bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,4,6-tri-tert-butylphenyl2-butyl-2-ethyl-
1,3-propanediol phosphate or bis(2,4-dicumylphenyl) pentaerythritol diphosphite,
30 hydroxylamines, such as
diethylhydroxylamine.
Secondary arylamines, such as N-(2-naphthy1)-N-phenylamine, 2,2,4-trimethyl-1,2-
PO01 00530-Foreim Countries
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d w q u i n o l i n e polymer (CAS No. 26780-96-I), N-2-propyl-N'-phenyl-p-phenylenediamine,
N-(I-naphthy1)-N-phenylamine, (benzenamine, N-phenyl-, reaction products with 2,4,4-
trimethylpentene) (CAS No. 684 1 1-46-l), 4-(1 -methyl-1 -phenylethyl)-N-[4-(1-methyl-1-
phenylethy1)phenyllaniline.
5 Lactones and benzofuranones, such as Irganox KP 136 (CAS No. 18 13 14-48-7).
Thioethers and thioesters, such as
distearyl3,3-thiodipropionate, dilauryl3,3'-thiodipropionate,d itetradecyl thiodipropionate,
di-n-octadecyl disulphide.
UV absorbers which may be mentioned are:
10 (methanone, [methylenebis(hydroxymethoxyphenylene)]bis[phenyl-), (methanone, [1,6-hexanediylbis[
oxy(2-hydroxy-4,l -phenylene)]]bis[phenyl-), 2-benzoyl-5-methoxyphenol, 2,4-dihydroxybenzophenone,
2,2'-dihydroxy.-4-methoxybenzophenone2,-h ydroxy-4-octyloxybenzophenone,
2-hydroxy-4-dodecyloxybenzophenone, 2-(2-hydroxy-4-hexyloxypheny1)-4,6-diphenyl-
1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-l,3 ,5 -triazine,
1 5 2-ethoxy-2'-ethyloxalic acid bisanilide, N-(5-tert-butyl-2-ethoxyphenyl)-N'-(2-ethylphenyl)-
oxamide, dimethyl (p-methoxybenzylidene)malonate, 2,2'-(1,4-phenylene)bis[3,1 -benzoxazin-
4-one], N'-(4-ethoxycarbonylphenyl)-N-methyl-N-phenylfomamidine4,- methoxycinnamic acid
2-ethylhexyl ester, 4-methoxycinnamic acid isoamyl ester, 2-phenylbenzimidazole-5-sulphonic
acid, 2-cyano-3,3-diphenylacrylica cid 2-ethylhexyl ester, 2-ethylhexyl salicylate or 3-(4-methyl-
20 benzy1idene)bornan-2-one,
chelators, such as
ethylenediaminetetraacetate (EDTA), ethylenediamine, acetylacetone, nitrotriacetic acid, ethylene
glycol bis(Baminoethy1 ether)-N,N-tetraacetic acid, 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine,
2,2',6',2"-terpyridine, 4,4'-diphenyl-2,2'-bipyridine, 2,2'-bipyridine-3,3'-diol, 1 , 1 0-phenanthroline,
25 4-methyl- 1 , 1 0-phenanthroline, 5-methyl- 1 , 1 0-phenanthroline, 4,7-dimethyl- 1 , 1 0-phenanthroline,
5,6-dimethyl-1,lO-phenanthroline, 3,4,7,8-tetramethyl-1 ,l0-phenanthroline, 4,7-diphenyl-
1 , 1 0-phenanthroline, 2,4,7,9-tetramethyl- 1, 1 0-phenanthroline, N,N,N',N'-tetramethylethylenediarnine,
2-hydroxyquinoline, 8-hydroxyquinoline, 2-hydroxy-4-methylquinaldine, 5-chloro-
8-hydroxyquinoline, 5,7-dichloro-8-hydroxyquinoline2,, 4-quinolinediol, 2-quinolinethiol,
PO01 00530-Foreign Countries
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phehino)ethane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane,
1,4-bis(diphenylphosphino)butane, polyaspartic acid or iminodisuccinate.
The aforementioned UV adsorbers and W stabilizers may or may not also be a constituent of the
compositions according to the invention.
5 The decomposition of iodine-containing biocides is promoted primarily in the presence of the
transition metal siccatives described in more detail above. Although the strongest decomposing
effects are observed in the presence of these transition metal siccatives, a series of other
components also have a destabilizing effect on iodine-containing biocides. Mention is to be made
here of inorganic and organic pigments, fillers, skin preventers, rheology additives such as, for
10 example, anti-settling agents and thixotropic agents, further compounds, in particular biocides such
as fungicides, bactericides, anti-fouling agents and algicides, solvents, process additives,
plasticizers, W stabilizers and heat stabilizers, corrosion inhibitors etc.
In the coating compositions according to the invention, the decomposition can surprisingly be
largely or completely avoided, an extension in the drying time compared to coating compositions
15 not equipped with microcapsules-comprising iodine-containing biocides and nitrogen-containing
inorganic carrier materials, so-called blank formulations, is not observed.
Consequently, without the applicant wanting to be committed thereto scientifically, a mechanism
other than a removal of metal ions presumably takes place, as is described for example with
polymers of aziridines for removing heavy metal ions from waste waters in DE-A1-1 96 27 909. A
20 removal of heavy metal ions would attenuate the effect of the transition metal siccatives and thus
extend the drying time of the coating compositions accordingly.
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Examples
Example 1 WBC Dispersion I)
150 g of a 50% strength by weight solution of a long-oil, thixotroped alkyd resin in isoparaffm
5 (Worlee S 6358; Worlee-Chemie GmbH, Lauenburg, Germany), which has firstly been stirred
smooth by stirring for 15 minutes on a dissolver at 8000 to 12 000 rpm and heating to 65OC, was
introduced and subsequently incorporated with 404.4 g of IPBC (iodpropynyl butylcarbamate) and
445.6 g of isoparaffin (Isopar L; boiling range 180 to 220°C) on a dissolver. After-stirring was
then carried out for 45 min at 3500 rpm on a dissolver.
10 The resulting thin-liquid dispersion was then ground twice using a bead mill (Dyno-Mill; Multilab,
300 ml grinding container with 80% fill level and zirconium oxide beads with a diameter of 0.4 to
0.6 mm). This gave 877 g of a white, thin-liquid dispersion.
Example 2 (Dispersion I with encapsulated IPBC)
15 5.52 g of a mixture of 1,6butanediol and trimethylolpropane (10:2) and 11.96 g of a 7.63%
strength by weight solution of Tanemul 508 (non-ionic surfactant based on
ethoxylated/propoxylated stearyl alcohol with an HLB value (HLB = hydrophilic lipophilic
balance) of ca. 13 in Isopar L were stirred for 10 min at 24 000 rpm on an Ultraturax with 60 g of
dispersion I from Example 1.
20 The mixture was then transferred to a 250 ml flask and, under a nitrogen protective gas and with
stirring, 1.32 g of catalyst (1% strength by weight solution of dibutyltin dilaurate in Isopar L) and a
solution of 12.4 g of tolyl2,4-diisocyanate (TDI) in 12.4 g of Isopar were added dropwise over the
course of 1.5 hours. Following a post-stirring time of 1.5 hours at room temperature, the mixture
was after-stirred for 1 hour at 40°C and for 48 h at room temperature. This gave 103.6 g of a-white
25 dispersion with an IPBC content of 23.17% by weight.
Example 3 (Dispersion 11 with encapsulated IPBC)
13.8 g of a mixture of 1,3-propanediol and trimethylolpropane (10:2) and 29.9 g of a 7.63% .
strength solution of Tanemul 508 in Isopar L were stirred for 10 min at 24 000 rpm on an
30 Ultraturax with 150 g of dispersion I from Example 1.
Then, the mixture was transferred to a 250 ml flask and, under a nitrogen protective gas and with
stirring, 6.6 g of catalyst (1% strength by weight solution of dibutyltin dilaurate in Isbpar L) and a
solution of 3 1.0 g of TDI in 3 1.0 g of Isopar L were added dropwise over the course of 1.5 hours.
Following a post-stirring time of 1.5 hours at room temperature, the mixture was after-stirred for
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1 at 40°C and for 48 h at room temperature. This gave 258.9 g of a white to pale yellow
dispersion with an IPBC content of 23.17% by weight.
Example 4 (Dispersion III with encapsulated IPBC)
5.52 g of a mixture of 1,3-propanediol and trimethylolpropane (2:l) and 11.96 g of a 7.63%
strength by weight solution of Tanemul 508 in Isopar L were stirred for 10 min at 24 000 rpm on
an Ultraturax with 60 g of dispersion I from Example 1.
Then, the mixture was transferred to a flask and, under nitrogen protective gas and with stirring,
1.32 g of catalyst (1% strength solution of dibutyltin dilaurate in Isopar L) and a solution of 12.0 g
of TDI in 12.0 g of Isopar L were added dropwise over the course of 1.5 hours. Following a poststirring
time of 20 min at room temperature, the mixture was stirred for a further 2 hours at 40°C.
A further 2.76 g of the mixture of 1,3-propanediol and trimethylolpropane (2:l) are added to the
resulting suspension and the mixture is turraxed for 10 min at 24 000 rpm. The mixture is cooled
to 16 to 1 8OC using an ice bath, a further 0.66 g of the aforementioned catalyst is added and then a
further 12.4 g of a 1:l mixture of TDI in Isopar L is metered in dropwise. The suspension, which
initially becomes thicker, was then after-stirred for one hour at 40°C and then for 16 hours at room
temperature.
n i s gave 119.42 g of a white to pale yellow dispersion with an IPBC content of 22.1% by weight.
Example 5 (Dispersion IV with encapsulated IPBC)
90 g of a 50% strength by weight solution of a long-oil, thixotroped alkyd resin in isoparaffin
(Worlee S 6358; Worlee-Chemie GmbH, Lauenburg, Germany), which was firstly stirred smooth
by stirring for 15 minutes on a dissolver at 8000 to 12 000 rpm and heating to 65OC, was
introduced and, in succession, incorporated with 242.7 g of IPBC, 5.52 g of guanidine carbonate,
61.1 g of ethylenediammonium dichloride and 200.7 g of isoparaffin (Isopar L; boiling range 180
to 220°C) on a dissolver. After-stirring was then carried out for 45 min at 3500 rpm on a dissolver.
This gave a very thin-liquid suspension. The dispersion obtained was then ground twice using a
bead mill (Dyno-Mill; Multilab, 300 ml grinding container with 80% fill level and zirconium oxide
beads with a diameter of 0.4 to 0.6 rnm). This gave 460 g of a white, thin-liquid dispersion, which
was left to ripen overnight.
60 g of the above suspension are introduced, admixed with 10 g of Isopar L and 3 drops of
ethylenediamine and then, after adding 14.8 g of a mixture of 50% by weight Desmodur N3400
(hexamethylene diisocyanate uretdione, CAS No. 23501-81-7), 42.37% by weight Isopar L and
7.63% by weight Tanemul KS, treated on an Ultraturrax at 24 000 rpm for 5 minutes. The mixture
was then stirred for 16 hours at 40°C. This gave 84.8 g of a white, thick-liquid dispersion with an
IPBC content of 28.3% by weight.
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+Es le 6 (Stabilizer I)
An oil phase consisting of 28.0 g of Crosslinker CX-100 from DSM (trirnethylolpropane tris[3-(2-
methyl-1-aziridiny1)propionatel and 7.78 g of Rhodiasolv@ DIB from Rhodia (mixture consisting
of diisobutyl adipate, diisobutyl glutarate and diisobutyl succinate) was emulsified for 10 minutes
with an emulsifier solution consisting of 1.78 g of ~anemul@K S from Tanatex (castor oil
ethoxylate with 30 eq. of EO) in 60 g of water under the action of an Ultraturrax (24 000 rpm). The
resulting colourless emulsion was added to a dispersion of 54.0 g of ~erosil@20 0 from Evonik
(fumed silica with a BET surface area of 200 m21g and a DBP absorption capacity of 300 dl00 g)
in 300 g of water with paddle stirring and then stirred for 24 hours.
The Aerosil laden with the aziridine and Rhodiasolv DIB was isolated from the resulting
dispersion by spray-drying (Biichi B-290 spray-dryer, pump output 60%, N2 flow rate 45 l*min-',
inlet 160°C, outlet 53 to 61°C). This gave 85 g of a very fine, colourless solid. The nitrogen
content was 2.00% by weight.
Example 7 (Stabilizer II)
An oil phase consisting of 14.0 g of Corial Harter AN from BASF (trirnethylolpropane tris[3-(1-
aziridiny1)propionatel and 3.89 g of ~hodiasolv@D IB from Rhodia (mixture consisting of
diisobutyl adipate, diisobutyl glutarate and diisobutyl succinate) was emulsified with an emulsifier
solution of 0.89 g of ~anemul@KS from Tanatex (castor oil ethoxylate with 30 eq. of EO) in
29.1 g of water under the action of an Ultraturrax (24 000 rpm) for 10 minutes. The resulting
colourless emulsion was metered into a dispersion of 27.0 g of ~erosil@20 0 from Evonik (fumed
silica with a BET surface area of 200 m21g and a DBP absorption capacity of 300 g/100 g) in 600 g
of water with paddle stirring and then stirred for 16 hours.
The Aerosil laden with the aziridine and Rhodiasolv DIB was isolated from the resulting
dispersion by spray-drying (Biichi B-290 spray-dryer, pump output 45%, N2 flow rate 45 l*min-',
inlet 160°C, outlet 59°C). This gave 34.77 g of a very fme, colourless solid and 3.5 g of a coarse
solid. The nitrogen content was 2.97% by weight.
Example 8 (Stabilizer IIl)
11.9 g of Corialhsirter AN from BASF (trimethylolpropane tris[3-(1-aziridiny1)propionatel are
dissolved in 8.1 g of water. The resulting colourless solution was metered into a dispersion of
27.0 g of ~erosil' 200 from Evonik (fumed silica with a BET surface area of 200 m21g and a DBP
absorption capacity of 300 dl00 g) in 591 g of water with paddle stirring and then stirred for
24 hours.
PO01 00530-Foreign Countries
- 47 -
Th erosil laden with the aziridine was isolated from the resulting dispersion V by spray-drying
(Biichi B-290 spray-dryer, pump output 45%, Nz flow 45 l*min-', inlet 160°C, outlet 59°C). This
gave 32.68 g of a very fine, colourless solid and 4.5 g of a coarse solid. The nitrogen content was
2.93% by weight.
5 Example 9 (Stabilized IPBC Dispersion, D-a
30 g of the dispersion from Example 2 were admixed with 10 g of Isopar L and 7.72 g of stabilizer
I from Example 6 and mixed for 10 min using the Ultraturax at 24 000 rpm. This gave a white
dispersion with a content of 14.57% by weight of IPBC.
10 Example 10 (Stabilized IPBC Dispersion, D-II)
30.1 g of the dispersion fiom Example 3 were admixed with 15 g of Isopar L and 7.62 g of
stabilizer 11 from Example 7 and mixed for 5 min with the Ultraturax at 24 000 rpm. This gave a
white dispersion with a content of 13.22% by weight of IPBC.
15 Example 11 (Stabilized IPBC Dispersion, D-IU)
30 g of the dispersion from Example 3 were admixed with 15 g of Isopar L and 7.65 g of stabilizer
III from Example 8 and mixed for 5 min with the Ultraturax at 24 000 rpm. This gave a white
dispersion with a content of 13.2% by weight of IPBC.
20 Example 12 (Stabilized IPBC Dispersion, D-IV)
100 g of the dispersion from Example 3 were admixed with 49.27 g of Isopar L and 27.74 g of
stabilizer I fiom Example 6 and mixed for 5 min with the Ultraturax at 24 000-rpm. This gave a
white dispersion with a content of 13.8% by weight of IPBC.
25 Example 13 (Stabilized IPBC Dispersion, D-V)
30 g of the dispersion from Example 4 were admixed with 10 g of Isopar L and 6.59 g of the
stabilizer from Example 6 and mixed for 10 min with the Ultraturax at 24 000 rpm. This gave a
white dispersion with a content of 13.6% by weight of IPBC. Storage of the dispersion at 40°C
revealed after 16 weeks only a slight cream-coloured discoloration and no measurable active
3 0 ingredient degradation.
Example 14 (Stabilized IPBC Dispersion, D-IT)
30 g of the dispersion from Example 5 were admixed with 20 g of Isopar L and 9.43 g of stabilizer
I from Example 6 and mixed for 10 min with the Ultraturax at 24 000 rpm. This gave a white
35 dispersion with a content of 14.3% IPBC. Storage of the dispersion at 40°C revealed after 4 weeks
PO0 1 00530-Foreign Countries
-48-
on)a slight cream-coloured discoloration and slight active ingredient degradation to 13.8% by
weight of IPBC.
Example 15 Use of the stabilized IPBC dispersions according to the invention in binder
5 formulations
The stabilized IPBC dispersions from Examples 9, 10, 1 1, 12, 13 and 14 were incorporated
into a typical alkyd-based coating system (alkyd stain A) in the presence of a transition
metal dryer (cobalt) and a metal oxide pigment (iron oxide).
As comparison, the alkyd stain A is admixed with pure IPBC (V-I) or with a non-inventively
10 stabilized IPBC (V-11a)s per Table 1.
I Rhodiasolv DIB* 1 55% by weight I
Table 1 - IPBCIAziridine concentrate (V-II)
* Mixture consisting of diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate, Rhodia.
**
Trimethylolpropane tris[3-(2-methyl-1-aziridiny1)propionatel
IPBC
Crosslinker CX-loo**
The formulation of the alkyd stains used is shown in Table 2.
30% by weight
15% by weight
15 To determine the stabilization, an accelerated ageing test was carried out. For this, the equipped
colour systems as per Table 2 were poured into tightly closing 200 ml glass bottles, with only a
minimum residual amount of air remaining in the package, and stored at 40°C. The results can be
found in Table 3.
PO0 1 00530-Foreign Countries
- 49 -
Tal) 2 Compositions of the alkyd stains A-I to A-VIIJ (all data in % by weight)
Ingredients
Alkyd resin
Vialkyd VAF 4349,
80 SD 60
(Cytec)
Solvent
Texan01 (Eastman)
Rheology additive
BYK E4 1 1 ( BYK)
Shellsol D60
(Shell Chemicals)
Pigment preparation
MK-Solcolor iron
oxide red 13 OM
(h4K Chemicals)
Siccative
0cta-soligena 69
(contains 6% cobalt)
(Borchers)
D-I
D-II
D-III
D-IV
v-I
V-II
D-V
D-VI
A-I
22.5
5.0
0.4
62.98
4.0
0.3
4.82''
-
-
-
A-II
22.5
5 .O
0.4
62.50
4 .O
0.3
-
5.30"
A-111
22.5
5.0
0.4
62.50
4.0
0.3
-
-
5.30"
-
-
A-V*
22.5
5.0
0.4
67.1
4.0
0.3
-
-
-
0.7
-
-
A-IV
22.5
5.0
0.4
62.73
4.0
0.3
-
-
-
5.07"
-
-
-
A-VI*
22.5
5.0
0.4
65.47
4.0
0.3
-
-
-
2.33"
-
-
A-VII
22.5
5.0
0.4
62.29
4.0
0.3
-
-
-
-
-
-
5.51''
-
A-VIII
22.5
5.0
0.4
62.70
4.0
0.3
-
-
-
-
-
-
-
5.10"
PO0 1 00530-Foreim Countries
* womparison
') corresponds in each case to a content of 0.7% by weight of IPBC, based on the stain
Texan01 is 2,2,4-trimethyl-1,3-diolm onoisobutyrate
Shellsol D60: is a hydrocarbon mixture of n-, iso- and cycloaliphatics with a boiling range from
5 193 to 245OC
Octasoligen 69 is here cobalt bis(2-ethylhexanoate)
BYK E4 1 1 is a rheology additive based on a modified urea
Table 3 Stability of the IPBC in the alkyd stains A-I to A-Vm at 40°C
I I Residual content of IPBC [%I based on the starting value
I Alkyd stain l I 1 Weeks 2 Weeks 4 Weeks I
A-I
A-11
A-IV
I A-VI* 1100 1100 1 1 O I
100
100
A-V*
100
n.d. = Data not determined
n.d.
n.d.
100
A-VII
A-VIII
10 Compared with an alkyd stain A-0, the alkyd stains A-I to A-IV and A-VII and A-VIII had no
extension in the drying time.
n.d.
Alkyd stain A-0 comprised:
100
93
96
100
100
100
72
100 8 8
52
n.d.
97.5
Alkyd resin Vialkyd VAF 4349, 80 SD 60 (Cytec)
Solvent Texan01 (Eastman)
Rheology additive BYK E4 1 1 (BYK)
Shellsol D60 (Shell Chemicals)
Pigment preparation- MJS-Solcolor iron oxide red 130M (MK
Chemicals)
Siccative 0cta-soligenB 69 (contains 6% cobalt) (Borchers)
0
22.5% by weight
5 .O% by weight
0.4% by weight
67.80% by weight
4.0% by weight
0.3% by weight
91.8
96.2
91.8
83.5

PO0 1 00530-Foreign Countries
Patent Claims
1. Composition comprising
microcapsules comprising at least one iodine-containing biocide
at least one nitrogen-containing inorganic carrier material.
5 2. Composition according to Claim 1 further comprising at least one nonpolar solvent.
3. Composition according to Claim 1 or 2, characterized in that the iodine-containing
biocides are selected from the group consisting of:
diiodomethyl p-tolyl sulphone, diiodomethyl p-chlorophenyl sulphone, 3-bromo-2,3-
diiodo-2-propenyl alcohol, 2,3,3-triiodoallyl alcohol, 4-chloro-2-(2-chloro-2-
methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone, iodofenfos, 3-iodo-2-
propynyl 2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl 4-chlorophenyl formal,
N-iodopropargyloxycarbonylalanine, N-iodopropargyloxycarbonylalanine ethyl ester, 3-(3-
iodopropargyl)benzoxazol-2-one, 3-(3-iodopropargy1)-6-chlorobenzoxazol-2- 3-iodo-
2-propynyl alcohol, 4-chlorophenyl 3-iodopropargyl formal, 3-iodo-2-propynyl
propylcarbamate, 3-iodo-2-propynyl butylcarbamate (IPBC), 3-iodo-2-propynyl
m-chlorophenylcarbamate, 3-iodo-2-propynyl phenylcarbamate, di(3-iodo-2-propynyl)
hexyldicarbamate, 3-iodo-2-propynyloxyethanol ethylcarbarnate, 3-iodo-2-
propynylowethanol phenylcarbamate, 3-iodo-2-propynyl thioxothioethylcarbamate,
3-iodo-2-propynyl carbarnate (PC), 3-bromo-2,3-diiodo-2-propenyl ethylcarbamate,
3-iodo-2-propynyl n-hexylcarbamate and 3-iodo-2-propynyl cyclohexylcarbamate and
compounds of the formula (I)
in which
R' is unsubstituted or substituted alkyl, alkenyl, alkynyl or phenyl.
25 4. Composition according to one of Claims 1 to 3, characterized in that the iodine-containing
bibcides are selected from the group consisting of 3-iodo-2-propynyl propylcarbamate,
3-iodo-2-propynyl butylcarbamate, 3-iodo-2-propynyl m-chlorophenylcarbamate, 3-iodo-2-
PO0 1 00530-Foreign Countries
-52-
) propynyl phenylcarbamate, di(3-iodo-2-propynyl) hexyldicarbamate, 3-iodo-2-
propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyloxyethanol phenylcarbamate,
3-iodo-2-propynyl thioxothioethylcarbarnate, 3-iodo-2-propynyl carbamate, 3-bromo-2,3-
diiodo-2-propenyl ethylcarbamate, 3-iodo-2-propynyl n-hexylcarbamate and 3-iodo-2-
propynyl cyclohexylcarbamate.
5. Composition according to one of Claims 1 to 4, characterized in that the iodine-containing
biocide is 3-iodo-2-propynyl butylcarbamate.
6. Composition according to one of Claims 1 to 5, characterized in that the microcapsules
comprise capsule materialswhich are selected fiom the group of polyureas, polyurethanes
and mixed polyurea-polyurethane compounds.
7. Composition according to one of Claims 1 to 6, characterized in that the nitrogencontaining
inorganic carrier materials have a nitrogen content of 0.05 to 10% by weight,
preferably of 0.1 to 10% by weight.
8. Composition according to one of Claims 1 to 7, characterized in that the nitrogen-
15 containing inorganic carrier materials have been prepared by reacting inorganic carrier
materials with at least one nitrogen-containing compound.
9. Composition according to Claim 8, characterized in that the nitrogen-containing
compounds are selected from the following:
A) mononitrogen compounds of the formula (II)
in which
R2, R3 and R4 in each case independently of one another are hydrogen, alkyl, alkenyl or
aryl or pairwise together form a 3 to 7 membered N-heterocyclic, aliphatic,
unsaturated or aromatic ring
where the radicals allcyl, alkenyl or aryl or the 3 to 7 membered
N-heterocyclic, aliphatic, unsaturated or aromatic ring are either
unsubstituted or mono- or polysubstituted by radicals which are selected
fiom the group hydroxyl, fluorine, chlorine, bromine, iodine, carboxyl,
alkylsulphonyl, arylsulphonyl, nitrile or isonitrile,
but where at least one of the radicals R ~R,3 and R~i s not hydrogen,
PO0 1 00530-Foreign Countries
9
B) polynitrogen compounds
C) aziridines.
10. Composition according to one of Claims 1 to 9, characterized in that it comprises one or
5 more further biocides which are selected fiom the following group:
triazoles such as:
azaconazole, azocyclotin, bitertanol, bromuconazole, cyproconazole, diclobutrazole,
difenoconazole, diniconazole, epoxyconazole, etaconazole, fenbuconazole, fenchlorazole,
fenethanil, fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole,
imibenconazole, ipconazole, isozofos, myclobutanil, metconazole, paclobutrazole,
penconazole, propioconazole, prothioconazole, simeconazole, (+)-cis-1-(4-chloropheny1)-
2-(1 H- 1,2,4-triazol- 1 -yl)cycloheptanol, 241 -tert-buty1)- 1 -(2-chloropheny1)-3-(1,2,4-triazol-
I-y1)propan-2-01, tebuconazole, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole,
triticonazole, uniconazole and their metal salts and acid adducts;
imidazoles such as:
clotrimazole, bifonazole, climbazole, econazole, fenapamil, imazalil, isoconazole,
ketoconazole, lombazole, miconazole, pefurazoate, prochloraz, triflumizole, thiazolcar,
l-imidazolyl-l-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one, and their metal salts and acid
adducts;
pyridines and pyrimidines such as:
ancymidol, buthiobate, fenarimol, mepanipyrin, nuarimol, pyroxyfur, triamirol;
succinate dehydrogenase inhibitors such as:
benodanil, carboxim, carboxim sulphoxide, cyclafluramid, fenfuram, flutanil, furcarbanil,
furmecyclox, mebenil, mepronil, methfuroxam, metsulphovax, nicobifen, pyracarbolid,
oxycarboxin, Shirlan, Seedvax;
naphthalene derivatives such as:
terbinafine, naftifine, butenafme, 3-chloro-7-(2-aza-2,7,7-trimethyloct-3-en-5-yne);
sulphenamides such as:
PO0 1 00530-Foreinn Countries
- 54 -
dichlofluanid, tolylfluanid, folpet, fluorofolpet; captan, captofol;
benzirnidazoles such as:
carbendazim, benomyl, fuberidazole, thiabendazole or their salts;
morpholine derivatives such as:
aldimorph, dimethomorph, dodemorph, falimorph, fenpropidin, fenpropimorph,
tridemorph, trimorphamid and their arylsulphonate salts such as, for example,
p-toluenesulphonic acid and p-dodecylphenylsulphonic acid;
benzothiazoles such as:
2-mercaptobenzothiazole;
benzothiophene dioxides such as:
N-cyclohexyl-benzo[b]thiophenecarboxamide S,S-dioxide;
benzamides such as:
2~6-dichloro-~-(4-trifluorometh~lbenz~l)beamitedcel,o ftalam;
boron compounds such as:
boric acid, boric esters, borax;
formaldehyde and formaldehyde-releasing compounds such as:
benzyl alcohol mono(poly)hemiformal, - 1,3-bis(hydroxymethy1)-
5,5-dimethylimidazolidine-2,4-dione (DMDMH), bisoxazolidine, n-butanol hemiformal,
cis-1- (3-chloroally1)-3,5,7-triaza-1- azoniaadamantane chloride, 1-[1,3-bis(hydroxymethy1-
2,5-dioxoimidazolidin-4-yl]-1,3-bis(hydroxymethyl)urea, dazomet, dimethylolurea,
4,4-dimethyloxazolidine, ethylene glycol hemiformal, 7-ethylbicyclooxazolidine,
hexahydro-S-triazine, hexamethylenetetramine, N-hydroxymethyl-NY-methylthiourea,
methylenebismorpholine, sodium N-(hydroxymethyl)glycinate,
N-methylolchloroacetamide, oxazolidine, paraformaldehyde, taurolin, tetrahydro-
1,3-oxazine, N-(2-hydroxypropyl)aminemethanol, tetramethylolacetylenediurea (TMAD); '
isothiazolinones such as:
N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisoPO0
1 00530-Foreign Countries
- 55 -
thiazolin-3-one, 5-chloro-N-octylisothiazolinone, N-octylisothiawlin-3-one, 4,5-
trimethyleneisothiazolinone, 43-benzoisothiazolinone;
aldehydes such as:
cimamaldehyde, formaldehyde, glutaraldehyde, R-bromocinnamaldehyde, ophthalaldehyde;
thiocyanates such as:
thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate;
quaternary ammonium compounds and guanidines such as:
benzalkonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium
chloride, dichlorobenzyldimethylalky1ammonium chloride,
didecyldimethylammonium chloride, dioctyldimethylammonium chloride,
N-hexadecyltrimethylammonium chloride, 1 -hexadecylpyridinium chloride, iminoctadine
tris(albesi1ate);
phenols such as:
tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol,3 ,5-dimethyl-4-chlorophenol,
dichlorophene, 2-benzyl-4-chlorophenol, triclosan, diclosan, hexachlorophene, methyl
p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl
p-hydroxybenzoate, octyl p-hydroxybenzoate, o-phenylphenol, m-phenylphenol,
p-phenylphenol, 4-(2-tert-butyl-4-methylphenoxy)phenol, 4-(2-isopropyl-4-
methylphenoxy)phenol, 4-(2,4Tdimethylphenoxy)phenol and their alkali metal salts and
alkaline earth metal salts;
microbicides with an activated halogen group such as:
bronopol, bronidox, 2-bromo-2-nitro-1,3 -propanediol, 2-bromo-4'-hydroxyacetophenone,
1 -bromo-3-chloro-4,4,5,5-tetramethyl-2-ione, R-bromo-R-nitrostyrene,
chloracetamide, chloramine T, 1,3-dibromo-4,4,5,5-tetramethyl-2-imidazoMnoneY
dichloramine T, 3,4-dichloro-(3H)- 1,2-dithiol-3 -one, 2,2-dibromo-3-nitrilepropionamide,
1,2-dibromo-2,4-dicyanobutane, halane, halazone, mucochloric acid, phenyl 2-
chlorocyanovinyl sulphone, phenyl 1,2-dichloro-2-cyanovinyl sulphone,
trichloroisocyanuric acid;
pyridines such as:
PO01 00530-Foreign Countries
-56-
1-hydroxy-2-pyridinethione (and the Cu, Na, Fe, Mn, Zn salts thereof), tetrachloro-4-
methylsulphonylpyridine, pyrimethanol, mepanipyrim, dipyrithion, 1-hydroxy-4-methyl-6-
(2,4,4-trimethylpenty1)-2(1H)-pyridine;
methoxyacrylates or similar such as:
azoxystrobin, dirnoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin,
orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, 2,4-dihydro-5-methoxy-2-
methyl-4-[2-[[[[I -[3-(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]phenyl]-3H-
1,2,4-triazol-3-one (CAS No. 185336-79-2);
metal soaps such as:
salts of the metals tin, copper and zinc with higher fatty acids, resin acids, naphthenic acids
and phosphoric acid, such as, for example, tin naphthenate, tin octoate, tin
2-ethylhexanoate, tin oleate, tin phosphate, tin benzoate, copper naphthenate, copper
octoate, copper 2-ethylhexanoate, copper oleate, copper phosphate, copper benzoate, zinc
naphthenate, zinc octoate, zinc 2-ethylhexanoate, zinc oleate, zinc phosphate, zinc
benzoate;
metal salts such as:
salts of the metals tin, copper, zinc, and also chromates and dichromates, such as, for
example, copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium
chromate, copper sulphate, copper chloride, copper borate, zinc fluorosilicate, copper
fluorosilicate;
oxides such as:
oxides of the metals tin, copper and zinc, such as, for example, tributyltin oxide, CuzO,
CuO, ZnO;
oxidizing agents such as:
hydrogen peroxide, peracetic acid, potassium persulphate;
dithiocarbamates such as:
cufraneb, ferban, potassium N-hydroxymethyl-N'-methyldithiocarbamate, sodium
dimethyldithiocarbamate, potassium dimethyldithiocarbarnate, mancozeb, maneb, metam,
metiram, thiram, zineb, zirarn;
PO0 1 00530-Foreign Countries
nitriles such as:
2,4,5,6-tetrachloroisophthalonitrile,d isodium cyanodithioimidocarbamate;
quinolines such as:
8-hydroxyquinoline and the copper salts thereof;
other fungicides and bactericides such as:
bethoxazin, 5-hydroxy-2(5H)-furanone, 4,5-benzodithiazolinone, 4,5-trimethylenedithiazolinone,
N-(2-p-chlorobenzoylethyl)hexaminium chloride, 2-oxo-2-(4-
hydroxyphenyl)acetohydroxycinnamoyl chloride, tris-N-(cyclohexyldiazeniumdioxy)-
aluminium, N-(cyclohexyldiazeniumdioxy)tributyltin or its potassium salts, bis-N-
(cyclohexyldiazeniumdioxy) copper, iprovalicarb, fenhexamide, spiroxamine,
carpropamid, diflumetorin, quinoxyfen, famoxadone, polyoxorim, acibenzolar S-methyl,
furametpyr, thifluzamide, methalaxyl-M, benthiavalicarb, metrafenon, cyflufenamid,
tiadinil, tea tree oil, phenoxyethanol,
Ag, Zn or Cu-containing zeolites alone or incorporated into polymeric materials.
Very especially preferred are mixtures with
azaconazole, bromuconazole, cyproconazole, dichlobutrazol, diniconazole, diuron, hexaconazole,
metaconazole, penconazole, propiconazole, tebuconazole, dichlofluanid,
tolylfluanid, fluorfolpet, methfuroxam, carboxin, N-cyclohexylbenzo[
b]thiophenecarboxamide S,S-dioxide, fenpiclonil, 4-(2,2-difluoro-1,3-benzodioxol-
4-y1)-1H-pyrrole-3-carbonitrile, butenafine, imazalil, N-methylisothiazolin-3-one,
5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, dichloro-N-octylisothiazolinone,
mercaptobenzothiazole, thiocyanatomethylthiobenzothiazole, thiabendazole,
benioisothiazolinone, N-(2-hydroxypropyl)aminomethanol, benzyl alcohol (hemi)formal,
N-methylolchloroacetamide, N-(2-hydroxypropyl)aminemethanol, glutaraldehyde,
omadine, Zn-omadine, dimethyl dicarbonate, 2-bromo-2-nitro- 1,3-propanediol, bethoxazin,
o-phthalaldehyde, 2,2-dibromo-3-nitrilepropionamide, 1,2-dibromo-2,4-dicyanobutane,
1,3-bis(hydroxymethyl)-5,5-dimethylimid~e-2,4-dione (DMDMH), tetramethylolacetylenediurea
(TMAD), ethylene glycol hemiformal, p-hydroxybenzoic acid,
carbendazirn, chlor~phen3, -methyl-4-chlorophenol,o -phenylphenol.
Apart from with the abovementioned fungicides and bactericides, mixtures with a good
efficacy are, moreover, also prepared with other active ingredients:
PO0 1 00530-Foreign Countries
insecticides / acaricides / nematicides:
abarnectin, acephate, acetamiprid, acetoprole, acrinathrin, alanycarb, aldicarb, aldoxycarb,
aldrin, allethrin, alpha-cypermethrin, amidoflumet, amitraz, avermectin, azadirachtin,
azinphos A, azinphos M, azocyclotin,
Bacillus thuringiensis, barthrin, 4-bromo-2-(4-chlorophenyl)-l-(ethoxymethyl)-5-(trifluoromethy1)-
lH-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin,
bifenthrin, bioresmethrin, bioallethrin, bistrilfluron, bromophos A, bromophos
M, bufencarb, buprofezin, butathiophos, butocarboxim, butoxycarboxim,
cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan, cartap, quinomethionate,
cloethocarb, chlordane, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron,
chlormephos, N-[(6-chloro-3-pyridinyl)methyl]-N'-cyano-N-methylethaneimidamide,
chlorpicrin, chlorpyrifos A, chlorpyrifos M, cis-resmethrin, clocythrin, clothiazoben,
cypophenothrin, clofentezin, coumaphos, cyanophos, cycloprothrin, cyfluthrin,
cyhalothrin, cyhexatin, cypermethrin, cyromazin,
decamethrin, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,
dialiphos, diazinon, 1,2-dibenzoyl- 1 (1,l -dimethyl)hydrazine, DNOC, dichlofenthion,
dichlorvos, dicliphos, dicrotophos, difethialone, diflubenzuron, dimethoate, 3,5-
dimethylphenyl methylcarbamate, dimethyl(pheny1)silyImethyl-3-phenoxybenzyl ether,
dimethyl(4-ethoxypheny1)silylmethyl-3 -phenoxybenzyl ether, dimethylvinphos,
dioxathion, disulphoton,
eflusilanate, emamectin, empenthrin, endosulphan, EPN, esfenvalerate, ethiofencarb,
ethion, ethofenprox, etrimphos, etoxazole, etobenzanid,
fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb,
fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fensulphothion,
fenthion, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron, flucycloxuron,
flucythrinate, flufenerim, flufenoxuron, flupyrazofos, flufenzine, flumethrin, flufenprox,
fluvalinate, fonophos, formethanate, formothion, fosmethilan, fosthiazate, fubfenprox,
furathiocarb,
halofenozide, HCH (CAS RN: 5 8-89-9), heptenophos, hexaflumuron, hexythiazox,
hydramethylnon, hydroprene,
imidacloprid, irniprothrin, indoxycarb, iprinomectin, iprobenfos, isazophos, isoamidophos,
isofenphos, isoprocarb, isoprothiolane, isoxathion, ivermectin,
PO0 1 00530-Foreign Countries
@ kadedrin,
lambda-cyhalothrin, lufenuron,
malathion, mecarbam, mervinphos, mesulphenphos, metaldehyde, methacrifos,
methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin,
monocrotophos, moxiectin,
naled, NI 125, nicotine, nitenpyram, noviflumuron,
omethoate, oxamyl, oxydemethon M, oxydeprofos,
parathion A, parathion M, penfluron, permethrin, 2-(4-phenoxyphenoxy)ethyl
ethylcarbamate, phenthoate, phorate, phosalon, phosmet, phosphamidon, phoxim,
pirimicarb, pirimiphos M, pirimiphos A, prallethrin, profenophos, promecarb, propaphos,
propoxur, prothiophos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion,
pyresmethrin, pyrethrum, pyridaben, pyridalyl, pyrimidifen, pyriproxifen, pyrithiobacsodium,
quinalphos,
resmethrin, rotenone,
salithion, sebufos, silafluofen, spinosad, spirodiclofen, spiromesifen, sulphotep, sulprofos,
tau-fluvalinate, taroils, tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron,
tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, tetramethrin, tetrarnethacarb,
thiacloprid, thiafenox, thiamethoxam, thiapronil, thiodicarb, thiofanox, thiazophos,
thiocyclam, thiomethon, thionazin, thuringiensin, tralomethrin, transfluthrin, triarathen,
triazophos, triazamate, triazuron, trichlorfon, triflumuron, trimethacarb,
vamidothion, xylylcarb, zetamethrin;
molluscicides:
fentin acetate, metaldehyde, methiocarb, niclosamide;
herbicides and algicides:
acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulphuron,
amitrole, ammonium sulphamate, anilofos, asulam, atrazine, azafenidin, aziptrotryne,
azimsulphuron,
PO0 1 00530-Foreign Countries
- 60 -
(C benazolin, benfluralin, benfuresate, bensulphuron, bensulphide, bentazone, benzofencap,
benzthiazuron, bifenox, bispyribac, bispyribac-sodium, borax, bromacil, bromobutide,
bromofenoxim, bromoxynil, butachlor, butamifos, butralin, butylate, bialaphos, benzoylprop,
bromobutide, butroxydim,
carbetamide, carfentrazone-ethyl, carfenstrole, chlomethoxyfen, chloramben,
chlorbromuron, chlorflurenol, chloridazon, chlorimuron, chlomitrofen, chloroacetic acid,
chloransulam-methyl, cinidon-ethyl, chlorotoluron, chloroxuron, chlorpropham,
chlorsulphuron, chlorthal, chlorthiamid, cinmethylin, cinosulphuron, clefoxydim,
clethodim, clomazone, chlomeprop, clopyralid, cyanamide, cyanazine, cycloate,
cycloxydim, chloroxynil, clodinafop-propargyl, cumyluron, clometoxyfen, cyhalofop,
cyhalofop-butyl, clopyrasuluron, cyclosulphamuron,
diclosulam, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat,
diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethipin,
dinitramine, dinoseb, dinoseb acetate, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr,
diuron, DNOC, DSMA, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham,
desmetryn, dicamba, dichlobenil, dimethamid, dithiopyr, dirnethametryn,
eglinazine, endothal, EPTC, esprocarb, ethalphluralin, ethidimuron, ethofumesate,
ethobenzanid, ethoxyfen, ethametsulphuron, ethoxysulphuron,
fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulphuron, fluazifop,
fluazifop-P, fuenachlor, fluchloralin, flufenacet, flumeturon, fluorocglycofen,
fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluroxypyr, fomesafen,
fosamine, fosametine, flamprop-isopropyl, flamprop-isopropyl-L, flufenpyr, flumicloracpentyl,
flumipropyn, flumioxzim, flurtamone, flumioxzim, flupyrsulphuron-methyl,
fluthiacet-methyl,
glyphosate, glufosinate-ammonium,
haloxyfop, hexazinone,
imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr, imazaquin, imazethapyr,
ioxynil, isopropalin, imazosulphuron, imazomox, isoxaflutole, imazapic,
ketospiradox,
lactofen, lenacil, linuron,
PO01 00530-Foreign Countries
- 61 -
MCPA, MCPA-hydrazide, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet,
mefluidide, mesosulphuron, metam, metamifop, metamitron, metazachlor,
methabenzthiazuron, methazole, methoroptryne, methyldymron, methyl isothiocyanate,
metobromuron, metoxuron, metribuzin, metsulphuron, molinate, monalide, monolinuron,
MSMA, metolachlor, metosulam, metobenzuron,
naproanilide, napropamide, naptalam, neburon, nicosulphuron, norflurazon, sodium
chlorate,
oxadiazon, oxyfluorfen, oxysulphuron, orbencarb, oryzalin, oxadiargyl,
propyzamide, prosulphocarb, pyrazolate, pyrazosulphuron, pyrazoxyfen, pyribenzoxim,
pyributicarb, pyridate, paraquat, pebulate, pendimethalin, pentachlorophenol, pentoxazone,
pentanochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor,
primisulphuron, prodiamine, profoxydim, prometryn, propachlor, propanil, propaquizafob,
propazine, propham, propisochlor, pyriminobac-methyl, pelargonic acid, pyrithiobac,
pyraflufen-ethyl,
quinmerac, quinocloamine, quizalofop, quizalofop-P, quinchlorac,
rirnsulphuron,
sethoxydim, sifuron, simazine, simetryn, sulphosulphuron, sulphometuron, sulphentrazone,
sulcotrione, sulphosate,
tar oils, TCA, TCA-sodium, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine,
terbutryn, thiazafluoron, thifensulphuron, thiobencarb, thiocarbazil, tralkoxydim, triallate,
triasulphuron, tribenuron, triclopyr, tridiphane, trietazine, trifluralin, tycor, thdiazimin,
thiazopyr, triflusulphuron,
vernolate.
11. Process for producing microcapsules comprising iodine-containing biocides, characterized
25 in that
a) a dispersion of at least one iodine-containing biocide and at least one alkyd resin in
a nonpolar solvent is admixed with an emulsion comprising a nonpolar solvent and at least
one compound selected from the group polyol, polyamine and amino alcohols,
b) and the mixture resulting according to step a) is reacted with at least one
polyisocyanate in the presence of catalyst.
PO01 00530-Foreign Countries
- 62 -
Process according to Claim 11, characterized in that the reaction according to step a) takes
place in the presence of at least one surfactant, the emulsion preferably comprising at least
one surfactant.
Industrial materials equipped with the compositions according to one of Claims 1 to 10.
Method for protecting industrial materials against infestation, alteration or decomposition
by microorganisms by treating the industrial materials with compositions according to one
of Claims 1 to 10.
Coating compositions comprising
at least one binder
*- microcapsules comprising at least one iodine-containing biocide
at least one nitroien-containing inorganic carrier material
at least one nonpolar solvent.
Coating compositions according to Claim 15, characterized in that they are paints,
varnishes, stains, primers or impregnation systems.
15 17. Coating compositions according to Claim 15 or 16, characterized in that they comprise at
least one transition metal siccative.