An organopolysiloxane composition having a microbiocidal action comprising an .alpha.,.omega.-dihydroxypolydiorganosiloxane and a benzimidazolyl-alkyl-carbamate of the formula ##STR1## wherein R.sup.1 is an alkyl radical with 1 to 4 carbon atoms, optionally substituted by the radical --OR.sup.3, PA1 R.sup.3 is an alkyl radical with 1 to 4 carbon atoms or the phenyl radical, and PA1 R.sup.2 is hydrogen, an alkyl radical with 1 to 4 carbon atoms, haolgen or nitro. Advantageously the carbamate is methylbenzimidazolylmethyl-carbamate, N-(fluorodichloromethylthio)-phthalimide, is present as a synergistic fungicide and the composition further comprises a silicon-containing crosslinking agent for the siloxane, a heavy metal salt or amino accellerant for crosslinking and an .alpha.,.omega.-bis-(trimethylsiloxy)-polydimethylsiloxane. Water per se or in atmospheric air cures the composition to a rubber elastic product resistant to microbes.

The invention relates to mixtures of organopolysiloxanes with specific 
crosslinking agents, which are plastically moldable and are provided with 
a microbicidal, and especially fungicidal, ingredient and which are 
converted in the presence of water or water vapor to a rubbery-elastic 
state. 
Such mixtures are used mainly as gap-filling putty and sealing compositions 
in the building trade, in sanitary installation and in the construction of 
aquaria. They all contain, as the base constituent, an 
.alpha.,.omega.-dihydroxypolydiorganosiloxane which is optionally mixed 
with a filler or other additives, such as pigments. If this is mixed with 
a silicon compound which contains at least three groups which are able to 
react both with silanol groups and with water and if the admittance of 
moisture is excluded, mixtures result which are stable on storage and 
which, on the admittance of atmospheric air, react, due to the water vapor 
content of the air, to give an elastomeric crosslinked product (compare, 
for example, W. Noll, Chemie u. Technologie der Silicone (Chemistry and 
Technology of Silicones), Verlag Chemie, Weinheim 1968, page 341 et seq.). 
Water-reactive silicon compounds having a crosslinking action of this type 
which are known and commonly used are, for example, alkoxy-, amino-, 
oximato-, acyloxy- or acylamido-silanes. The multiplicity of these 
crosslinking agents offers the welcome possibility of adaptation to the 
particular technical requirements, with regard to processing, adhesion to 
the given substrate and mechanical properties. 
The rate and the course of these reactions are, if necessary, influenced by 
additions of catalysts or other substances. Sometimes substances to 
improve the adhesion of the crosslinked organopolysiloxane elastomer to 
different substrates are also added to these compositions. 
The abovementioned substances are now mixed in diverse devices to give a 
paste containing polymer, fillers, plasticizer and additives, which is 
stable on storage in the absence of moisture and is converted to an 
elastomer only on the admittance of moisture. 
A common feature of all of these rubbery-elastic products is that, 
particularly when they are used in the sanitary field, they are frequently 
attacked by fungi and other micro-organisms. Unpleasant accompanying 
phenomena of this type manifest themselves, for example, as fungal attack 
on rubber seals on baths, showers, toilets and washbasins. These are 
discolored and become stained and of unpleasant appearance. 
For a long time now attempts have been made to eliminate this phenomenom by 
mixing into the paste further additives which have a known microbicidal 
action. However, these substances are mostly very complicated compounds, 
which, in the abovementioned mixture, may not change during storage and 
under transport conditions, sometimes up to 50.degree. C., and which is 
even more difficult, may not adversely influence the crosslinking 
mechanism and the properties (color, adhesion, degree of crosslinking) of 
the paste and of the crosslinked product. Amongst the currently available 
fungicides it was not possible to find one which can be employed without 
trouble with all of the crosslinking agents used for the systems mentioned 
here and which is not associated with disadvantages of some kind. 
Surprisingly, substances have now been found which can be employed in all 
of the abovementioned crosslinking systems, do not interfere in the 
crosslinking mechanism, even when the paste which has not been crosslinked 
is stored for a prolonged period, do not influence the color, adhesion and 
mechanical properties of the crosslinked product and have a very good 
fungicidal action and which, in combination with crosslinking agents or 
with the organopolysiloxanes, are mixed into the paste. 
Accordingly, the invention relates to plastic organopolysiloxane moulding 
compositions which have a microbicidal, and especially a fungicidal, 
action and are storable with the exclusion of water and which under the 
action of water or atmospheric air are already converted at room 
temperature into rubbery-elastic moldings or coatings, prepared by mixing 
.alpha.,.omega.-dihydroxypolydiorganosiloxanes with silicon compounds 
which serve as crosslinking agents and, optionally with 
.alpha.,.omega.-bis-(trimethylsiloxy)-polydimethylsiloxanes, with fillers 
and with heavy metal salts or amines which are known to accelerate the 
crosslinking, which are characterized in that they contain a 
benzimidazolyl-alkyl-carbamate of the general formula 
##STR2## 
wherein 
R.sup.1 denotes an alkyl radical with 1 to 4 carbon atoms, which is 
optionally substituted by the radical --OR.sup.3, 
where 
R.sup.3 represents an alkyl radical with 1 to 4 carbon atoms or the phenyl 
radical, and 
R.sup.2 denotes hydrogen, an alkyl radical with 1 to 4 carbon atoms, 
halogen or the nitro group, 
and also, optionally, further substances having a fungicidal action. 
The preparation of the benzimidazolyl-alkyl-carbamates is already known 
(compare, for example, U.S. Pat. No. 3,010,968). 
The following compounds may be mentioned as examples of 
benzimidazolyl-alkyl-carbamates: benzimidazolyl-methyl-carbamate, 
4-methyl-benzimidazolyl-methyl-carbamate, 
5-methyl-benzimidazolyl-methyl-carbamate, benzimidazolyl-ethyl-carbamate, 
4-methyl-benzimidazolyl-ethyl-carbamate, 
benzimidazolyl-isopropyl-carbamate, 
4-ethyl-benzimidazolyl-isopropyl-carbamate, 
5-methyl-benzimidazolyl-isopropyl-carbamate, 
4-propyl-benzimidazolyl-isopropyl-carbamate, 
4-butyl-benzimidazolyl-isopropyl-carbamate, 
4-isobutyl-benzimidazolyl-isopropyl-carbamate, 
benzimidazolyl-ethylmethoxy-carbamate, 
4-methyl-benzimidazolyl-methoxyethyl-carbamate, 
5-methyl-benzimidazolylmethoxyethyl-carbamate, 
benzimidazolyl-ethoxyethyl-carbamate, 
benzimidazolyl-propoxyethyl-carbamate, 
benzimidazolyl-phenoxyethyl-carbamate, 
4-methyl-benzimidazolyl-phenoxyethyl-carbamate and 
5-methyl-benzimidazolyl-phenoxyethyl-carbamate. 
The preferred benzimidazolyl-alkyl-carbamate is 
benzimidazolyl-methyl-carbamate. 
It is also possible to employ mixtures of different 
benzimidazolyl-alkyl-carbamates. 
In addition to the benzimidazolyl-alkyl-carbamates, yet further substances 
having a fungicidal action can be incorporated. In some cases synergistic 
effects can then arise. Examples of such further additives can be: 
halogenomethylthiophthalimides, such as, for example, 
N-(fluorodichloromethyl-thio)-phthalimides, 
N-dimethyl-N'-phenyl-(N'-fluorodichloromethyl-thio)-sulphamide, 
tetramethylthiurami-disulphide, tetraethylthiuram disulphide or 
1-methylol-2-thiono-1,2-dihydrobenzthiazole. 
These additives are employed in amounts such that there are about 1 to 25 
parts by weight of the additive per 1 part by weight of 
benzimidazolyl-alkyl-carbamate. 
The fungicidal substance added is a total of about 0.01-2% by weight, based 
on the total mixture. About 0.1-0.5% by weight is preferred. The agents 
having a fungicidal action can optionally also be added to the 
organopolysiloxanes as a solution in solvents, for example in dioxane. In 
general, the agent having a fungicidal action can also be incorporated as 
a solid with a very small particle size (100-350 microns). However, it is 
also possible to incorporate the fungicide in the form of a paste, for 
example in a silicone oil (for example polydimethylsiloxane oil). 
The active compounds employed according to the invention are active, for 
example, against the following fungi: Penicillium species, such as 
Penicillium glaucum, Penicillium funiculosum, Penicillium citrinum and 
Penicillium camerunense, Mucor species, such as Mucor racemosus, Rhicopus 
species, such as Rhicopus nigricans, Pullularia species, such as 
Pullularia pullulans, Chaetomium species, such as Chaetomium globosum, 
Geotrichum species, such as Geotrichum candidum, Trichoderma species, such 
as Trichoderma viride, Aspergillus species, such as Aspergillus flavus, 
Aspergillus terreus and Aspergillus niger, and Coniophora species, such as 
Coniophora cerebella. In addition, these substances also act against 
yeasts, such as, for example, Candida crusei and Candida albicans, and 
against algae and other micro-organisms.

The present invention will now be explained in even more detail with the 
aid of the examples which follow: 
EXAMPLE 1 
A mixture of 60 g of .alpha.,.omega.-dihydroxypolydimethylsiloxane with a 
viscosity of 50,000 cP and 25 g of 
.alpha.,.omega.-bis-(trimethylsiloxy)-polydimethylsiloxane with a 
viscosity of 1,300 cP is initially introduced. 4 g of 
ethyltriacetoxysilane are added to this mixture at room temperature and 
the resulting mixture is stirred briefly. 1.5 g of titanium dioxide and 
9.5 g of a finely dispersed silica and also 0.3 g of a mixture of 6 parts 
by weight of N-(fluorodichloromethylthio)-phthalimide and 1 part by weight 
of methylbenzimidazolyl-methylcarbamate are now added. The mixture is 
stirred in a planetary stirrer until it is homogeneous, which is the case 
after about 20 minutes. Finally, small amounts of a catalyst, in this 
case, for example, 5 mg of dibutyl-tin diacetate, are added and stirred in 
homogeneously for 10 minutes in vacuo. Evacuation is appropriate, in order 
to be able to fill the composition, after the mixing operation, 
homogeneously into a storage container (tube or cartridge). 
In order to test the storage stability, the molding composition according 
to the invention was stored, after the paste had been filled into tubes 
with the exclusion of air, for 8 weeks at 50.degree. C. and then spread 
out about 2 mm thick and completely cured by atmospheric humidity (65% 
relative atmospheric humidity) in about one day to give a rubber sheet. In 
contrast to the other fungicides, the sheet was snow white and shows no 
discoloration whatsoever, despite the paste having been stored at 
50.degree. C. (which corresponds to a storage stability, demanded in 
practice, of about 1/2 year at changing room temperatures). 
A rubbery-elastic skin of this type has approximately the following 
mechanical properties, both before and after storage: modulus of 
elasticity 100%, about 0.4 MPa, tensile strength about 1.4 MPa, elongation 
at break about 600% and Shore A hardness about 22. 
This rubber skin was not tested by the inhibition zone test according to 
Wallhauser (Deutscher Farberkalender 1970, pages 324-344, F. Eder Verlag, 
Frankfurt/M.) and excellent results were found. An inhibition zone of more 
than 5 mm had formed around the sample and even after the latter had been 
leached for 120 hours, this zone was still mold-resistant. 
An outstanding fungus-repellent action, compared with compositions not 
provided with a fungistatic ingredient, was also observed in the so-called 
soil rotting test (garden compost soil adjusted to pH 7 with sand and 
lime, at 22.degree. C. and approximately 90% relative atmospheric humidity 
with mold cultures and mold salt solutions). 
EXAMPLE 2 
A mixture of 45 parts by weight of 
.alpha.,.omega.-dihydroxypolydimethylsiloxane with a viscosity of 50,000 
cP and 20 parts by weight of 
.alpha.,.omega.-bis-(trimethyl-siloxy)-polydimethylsiloxane with a 
viscosity of 1,300 cP is initially introduced. 5 parts by weight of 
di(ethyl acetoacetate)-diisobutyl-titanol are added at room temperature 
and mixing is carried out for about 5 minutes at room temperature. 5 parts 
by weight of a finely disperse silica, 20 parts by weight of chalk, 2 
parts by weight of white pigment (TiO.sub.2) and 0.1 part by weight of 
carbon black are added to this mixture and the mixture is then stirred in 
a planetary stirrer, in vacuo, until it is homogeneous. 1 part by weight 
of a fungicide paste (consisting of 60 parts by weight of 
.alpha.,.omega.-bis-(trimethylsiloxy)-polydemethylsiloxane, 1 part by 
weight of dioxane, 5 parts by weight of highly disperse silica and 30 
parts by weight of a mixture consisting of 6 parts by weight of 
N-(fluorodichloromethylthio)-phthalimide and 1 part by weight of 
methylbenzimidazolyl-methyl-carbamate) and also 1 part by weight of 
dibutyl-tin dimaleate, as the catalyst, are now added, the mixture is 
stirred for about 10 minutes and 4 parts by weight of 
di-(N-methylbenzamido)-methylethoxysilane are now added to the total 
mixture and mixing is carried out in vacuo for 15 minutes. The further 
treatment is carried out as in Example 1. 
The mechanical properties (both before and after storage) were: modulus of 
elasticity 100%, about 0.14 MPa, tensile strength about 0.7 MPa, 
elongation at break about 550% and Shore A hardness about 12. 
A very good fungistatic action was determined with this system also. 
In will be appreciated that the instant specification and examples are set 
forth by way of illustration and not limitation, and that various 
modifications and changes may be made without departing from the spirit 
and scope of the present invention.