Fungicidal detergent composition

A fungicidal detergent concentrate contains a water soluble organic carboxylic acid, a zinc salt, e.g. zinc sulfate, a modified phthalic glycerol alkyd resin wetting agent-dispersant and conventional cleaning additives that function as degreasants, penetrants, surfactants, and the like. Optionally, the composition may contain a bleach, e.g. calcium hypochlorite or sodium hypochlorite or hydrogen peroxide. A method is also provided for removing mold and mildew from surfaces which comprises the steps mixing the concentrate with water and bleach and using the diluted mixture to clean the mold and mildew from the surface.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to detergent compositions of cleaning 
surfaces and destroying and preventing the regrowth of mold and mildew. 
In many areas of the world, the unwanted growth of mold and mildew is an 
annoying problem. The rapid growth of mold and mildew on surfaces, such as 
house walls, bathroom walls, and the like, is particularly troublesome in 
hot, humid climates. 
Prior to the prevent invention, once mold and mildew appeared on a surface 
it was not only very difficult to remove but its regrowth was almost 
certain. 
A costly problem occurs when mold and mildew is present on a surface that 
needs to be painted. In order to paint or repaint properly a surface that 
has become infested with mold or mildew, it is necessary to remove the 
mold and mildew completely. Prior to the present invention, the most 
widely used method for removing mold and mildew was to scrub vigorously 
the infected area until the mold and mildew was removed. Indeed, it is 
believed that prior to the present invention, no product was available 
that would instantly kill or remove mold and mildew without vigorous 
scrubbing. 
2. Brief Description of the Prior Art 
Halvorson et al. U.S. Pat. No. 2,138,805 discloses the incorporation of 
germicides in detergent compositions. 
Werntz U.S. Pat. No. 2,473,460 discloses detergent compositions containing 
bleaching agents. 
Fazzalari U.S. Pat. No. 3,992,146 discloses the use of copper sulfate as a 
bilcidal agent. 
Shibe et al. U.S. Pat. No. 3,272,751 discloses cleaning compositions 
containing certain zinc halide complexes. 
Chemical Abstracts 46, 6786 discloses fungicidal properties of acetic acid. 
Chemical Abstracts 57, 12950 discloses the use of hydrogen peroxide or 
sodium hypochlorite or calcium hypochlorite for sterilizing seeds. 
None of this prior art discloses detergent compositions containing 
fungicides which are retained on the surface cleaned to remove and inhibit 
regrowth of mold and mildew. 
SUMMARY OF THE INVENTION 
In this invention, a concentrate is provided which, when admixed with an 
oxidizing agent and used to clean an infested surface removes and inhibits 
regrowth of mold and mildew. The concentrate includes an organic acid, 
such as acetic acid or the like, a water soluble zinc salt, such as zinc 
sulfate, a modification phthalic glycerol alkyd resin wetting 
agent-dispersant, and conventional cleaning additives that function as 
degreasants, penetrants, surfactants, and the like. Optionally, the 
composition may contain a bleach, e.g. calcium hypochlorite or sodium 
hypochlorite or hydrogen peroxide. 
Accordingly, it is one object of the present invention to provide a novel 
detergent composition for removing mold and mildew from a surface and 
inhibiting regrowth thereon. 
Another object of the invention is provide a novel method for removing mold 
and mildew from an infested surface and inhibiting regrowth thereon. 
Other objects of this invention will be apparent from time to time 
throughout the specification and claims as hereinafter related. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The fungicidal or mold and mildew inhibiting detergent composition of the 
present invention is a mixture containing an organic acid, a zinc salt, 
such as zinc sulfate, a polymeric wetting agent-disperant, and various 
detergents and surfactants. 
The concentrate is prepared by adding a quantity of water to a mixing 
vessel and thereafter adding a water soluble organic acid to the water in 
the vessel. The water and organic acid are the mixed to provide a 
homogenous solution. 
In a separate vessel, or mixing zone, a cleaning solution is prepared. The 
cleaning solution contains ingredients which function as degreasants, 
penetrants, surfactants and wetting agents which will be described more 
fully hereinafter. These agents are dissolved in water to form a solution. 
The cleaning solution is then added to and mixed with the solution of 
organic acid in the mixing vessel. An alkali or alkaline earth metal 
tripolyphosphate may be included as the degreasant in the cleaning 
solution or may be added to the mixing vessel after the cleaning solution 
is added. A water solution of a fungicide is then added to the mixing 
vessel. All of the constituents in the mixing vessel are then mixed to 
yield a homogenous concentrate. 
Prior art cleaning compositions, which contain various additives, are 
disclosed in U.S. Pat. Nos. 2,138,805; 2,473,460; 2,645,615 and 3,282,852. 
In accordance with the present invention, the preferred organic acid for 
incorporation into the mold and mildew remover concentrate is acetic acid, 
and preferably, naturally occurring acetic acid such as vinegar. Other 
water soluble lower aliphatic carboxylic acids which may be used in the 
concentrate are formic, propionic, n-butanoic, n-pentanoic, 
trimethylacetic, n-hexanoic, lactic, methoxyacetic, cyanoacetic, 
chloroacetic, citric, partaric, etc. 
A typical degreasant which is used in the cleaning solution is sodium 
metasilicate. The penetrants are materials which penetrate oily, dirty 
surfaces such as alkanolamide detergents and the tetrasodium salt of 
ethyldiaminetetraacetic acid (EDTA). The surfactants which are used in the 
cleaning solution are preferably of the nonionic detergent or fatty 
alcohol type, although cationic and anionic detergents and sodium soaps of 
fatty acids may be used with lesser efficiency. An alkali metal or 
alkaline earth metal tripolyphosphate may serve as the degreasant in the 
cleaning solution or may be included as an additional ingredient in the 
concentrate to function as a degreasant and a water softener. 
The fungicides used in the concentrate are water soluble zinc salts, e.g. 
zinc sulfate, zinc acetate, zinc bromide, zinc chloride, zinc iodide, zinc 
nitrate, zinc bromate, and zinc chlorate. Zinc sulfate is preferred. 
The wetting agent used is a polymeric wetting agent-dispersant which 
disperses the ingredients and wets the surface being treated but when dry 
resists rewetting and removal of the fungicidal ingredient. A preferred 
wetting agent is a commercially available modified phthalic glycerol alkyd 
resin, TRITON B-1956 (identified by the manufacturer as a nonionic 
surfactant manufactured by reaction of polyglycerol with phthalic 
anhydride). 
The ingredients of the mold and mildew remover concentrate may be present 
in the range in set forth in Table 1 below. 
TABLE 1 
______________________________________ 
Ingredient Range in % by Weight 
______________________________________ 
Water 97.75-82.40 
Organic Acid 2.0-10.0 
Degreasant 0-2.0 
Penetrant 0-0.8 
Surfactant 0.1-1.0 
Wetting Agent 0.05-1.0 
Tripolyphosphate 0-0.8 
Fungicide 0.2-2.0 
______________________________________ 
The combination of cleaning ingredients in the mold and mildew remover 
concentrate is essential in order to kill mold and mildew and prevent 
regrowth. This is particularly true since most surfaces to be treated have 
an accumulation of dirt and grease in addition to a growth of mold and 
mildew thereon. It should be apparent that the function of the cleaning 
solution is to cut through the dirt and grease and allow the fungicidal 
ingredients to kill the mold and mildew. In this regard, a preferred 
composition for the mold and mildew remover concentrate is shown in Table 
2 below. 
TABLE 2 
______________________________________ 
Ingredient Percentage by Weight 
______________________________________ 
Water 93.6 
Organic Acid (Acetic Acid) 
3.56 
Degreasant (Sodium Metasilicate) 
0.76 
Penetrants (EDTA and Ethanolamide 
0.57 
Surfactants (Nonionic) 
0.38 
Wetting Agent (TRITON B-1956) 
0.19 
Sodiumtriphosphate 0.38 
Zinc Sulfate 1.00 
______________________________________

The procedure for preparing the mold and mildew concentrate of the present 
invention is further illustrated by the following examples: 
EXAMPLE 1 
Twenty gallons of water is added to a barrel having a 55-gallon capacity. 
Twenty-four gallons of vinegar is then added to the barrel. The vinegar 
has an acetic acid content of 10% by weight. The ingredients are mixed 
thoroughly to yield a homogenous acid solution. 
To prepare the cleaning solution, into a separate mixing vessel having at 
least a 2-gallon capacity, the following ingredients are admixed: Sodium 
metasilicate, tetrasodium salt of ethyldiaminetetraacetic acid (EDTA), an 
alkanolamide detergent, a linear alkoxypolyoxy alkyene ethanol surfactant 
and water. 
The following ingredients are added to the separate mixing vessel in an 
amount ot yield a cleaning solution having the composition in percent by 
weight as set forth in Table 3 below: 
TABLE 3 
______________________________________ 
Ingredient Percentage by Weight 
______________________________________ 
Sodium Metasilicate 20 
Tetrasodium EDTA 10 
Modified Phthalic Glycerol Alkyd Resin- 
Wetting Agent 5 
Alkanolamide Detergent 
5 
Linear Alkoxypolyoxyl alkyene ethanol 
10 
Water 50 
______________________________________ 
The tetrasodium salt of ethylaminediaminetetraacetic acid (EDTA) used in 
Example 1 was obtained from the Dow Chemical Co., Midland, Michigan, under 
the trademark Versene Powder. The alkanolamide detergent was obtained from 
the Stepan Chemical Co., under their designation Ninol 1285. The Ninol 
1285 detergent is an alkanolamide (a C1-C3 alkanolamide of a fatty acid) 
with excellent degreasing properties. The linear alkoxypolyoxy alkyene 
ethanol used is a product manufactured by the Stepan Chemical Company 
under the designation of Stepan EA-10. This Stepan EA-10 surfactant is a 
high foaming biodegradable nonionic surfactant. 
The foregoing ingredients are diluted and mixed with water to yeild 2 
gallons of cleaning solution containing about 50% water by weight. Two 
gallons of the cleaning solution is then added to the solution of acetic 
acid in the mixing vessel. Thereafter, 2 gallons of sodiumtripolyphosphate 
in water is added to the mixing vessel. The amount of 
sodiumtripolyphosphate in the solution to yield a detergent concentrate 
containing 0.38% wt. sodiumtripolyphosphate as set forth in Table 2 above. 
In another mixing zone, 5 pounds zinc sulfate (tetrahydrate) is dissolved 
in 5-gallons of hot (180.degree. F.) water and then added to the mixing 
vessel. 
The ingredients in the mixing vessel are then mixed to yield a homogenous 
solution. The chemical analysis of the resulting concentrate made by the 
foregoing procedure is set forth in Table 4 below: 
TABLE 4 
______________________________________ 
Function Ingredient Percentage by Wt. 
______________________________________ 
Organic Acid 
Acetic Acid 3.56 
Degreasant Sodiummetasilicate 
0.76 
Penetrant Tetrasodium (EDTA) 
0.38 
Wetting Agent 
TRITON B-1956 0.19 
Surfactant Stepan EA-10 0.38 
Penetrant NINOL 1285 0.19 
Fungicide Zinc Sulfate 1.00 
Water Softener 
Sodiumtripolyphosphate 
0.38 
Diluent Water 93.16 
______________________________________ 
As shown in Example 1, the concentrate of the present invention includes a 
cleaning solution. In other embodiments of the invention, the cleaning 
solution may include, in addition to the other constituents, a higher 
alkyl aryl sulfonate detergent, a multi-branched higher alkyl 
polyoxyethylene ethanol and an alkanolamine detergent. 
A cleaning solution of superior properties can be formulated which includes 
about 10-40% wt. of a mixture of a water soluble higher alkyl mononuclear 
aryl sulfonate salt having about 8-15 carbon atoms in the alkyl group and 
a multi-branched alkyl polyoxyethylene ethanol surfactant having about 
8-18 carbon atoms in said alkyl group and an average of about 5-30 
ethyleneoxide groups, the ratio of said sulfonate to polyethoxamer being 
from about 10:1 to about 1:4 by weight with at least about 3% of each 
material present in the composition. About 5-20% wt. of a water soluble 
alkanolamine or alkanolamide having 2-3 carbons in the alkanol group 
should also be present in the cleaning solution. This solution may be 
mixed with the wetting agent and fungicide salt, as described above, and 
may be diluted by admixture with the dilute aqueous solution of acetic 
acid. 
EXAMPLE 2 
In an alternant embodiment of the invention, a concentrate otherwise 
similar to the embodiment of Example 1 contains a cleaning solution which 
includes an alkaline metal higher alkyl benzene sulfonate, multi-branched 
tridecyl polyoxyethylene ethanol and triethanolamine. 
With regard to the higher alkyl mononuclear aryl sulfonate detergent, it is 
preferred to use the higher alkyl benzene sulfonates, however, other 
similar detergents having a mononuclear aryl group derived from toluene or 
xylene may be also used. The aryl nuculeus has at least one alkyl 
substituent having an average number of about 8-15 carbons and preferably 
about 12-15 carbons. The alkyl group may be branched and is usually 
derived from polymers of lower mono-olefins. A commercial tridecyl benzene 
contains a mixture of propylene polymers averaging about 13 carbons. The 
alkyl group may be straight chain such as n-decyl, dodecyl and tridecyl. 
The higher alkyl aryl sulfonate detergent material is employment preferably 
in the form of its alkali metal salt, particularly the sodium salt. Other 
water soluble salts may be used such as the potassium salt and ammonium 
salt. 
The alky polyethoxamer is prepared usually by the reaction of the higher 
aliphatic alcohols having 8-18 carbons with a predetermined proportion, 
within the range of 5 to 30 moles, of ethyleneoxide in order to obtain a 
product having the desired physical properties and performance 
characteristics. Satisfactory results are obtained with polyethoxamers 
(preferably 10-20 moles of ethyleneoxide) of multi-branched higher 
alcohols (preferably containing 11-15 carbons) such as produced by the Oxo 
process, well known in the art. This process involves the reaction of a 
multi-branched olefin of 7-17 carbons (e.g. tri-, tetra-, pentapropylene 
and di-isobutalene) with carbon monoxide and hydrogen to form the 
corresponding aldehyde, followed by reduction to the corresponding primary 
alcohol. Similar alcohols may be obtained by other processes however. The 
polyethoxomer of tridecyl alcohol (corresponding to alcohol produced from 
tetrapropylene and/or triisobutylene by the Oxo process) is particularly 
satisfactory. The optimum proportion of condensed ethyleneoxide varies 
with the type of alcohol so as to produce a suitable water soluble 
derivative having the desired solubilizing detergent and foaming effects. 
As indicated, the preferred of ethyleneoxide to alcohol corresponds to the 
reaction product of an average of 10-20 moles ethyleneoxide with tridecyl 
alcohol. 
The alkanolamines and alkanolamides have one or more hydroxy alkyl groups 
of 2-3 carbons, such as mono-, di- or triethanolamine isopropanol amine or 
the like. Good results are obtained when triethanolamine is employed which 
in commercial form may contain small amounts of mono- and diethanolamine. 
The alkanolamine or alkanolamide used is considered to be essentially in 
free form so as to be available for its necessary contribution. Where 
alkyolamine detergent salts are employed, an excess of alkanolamine should 
be used of the pH adjusted with caustic soda or the like so as to release 
or otherwise render effective the alkanolamine in the composition. In 
general, the pH of the final cleaning solution is at least about 9, 
usually in the range of about 9.5-12, and preferably from 10-11.5. 
The desirable qualities of the cleaning solution are a result of the mutual 
effects or interaction of the ingredients in proper proportions in the 
combination. The alkyl benzene sulfonate detergent, the polyethoxyamer, 
and the alkanolamine or alkanolamide detergent contribute to the desired 
properties of the system. As indicated, the total amount of sulfonate 
detergent and polyethoxamer is within the range of 10-40%, preferably 
20-30% of the liquid. The ratio of sulfonate to polyethoxyamer is selected 
from a range of about 10:1 to 1:4, preferably 5:1 to 1:1 with at least 3% 
of each in the liquid. The alkanolamine or alkanolamide is about 5-20%, 
preferably 7-12% of the composition. In general, the combination of the 
sulfonate detergent and polyethyoxyamer yields improved detergency as 
compared to similar products having only one of these materials in the 
same total concentration. 
The cleaning solution is prepared in any suitable manner by admixture at 
room temperature or reasonably elevated temperatures depending upon the 
specific ingredients used. A preferred method utilizes room temperature 
for admixing the main ingredients to a homogenous solution. This procedure 
involves preparing an aqueous slurry of the alkyl benzene sulfonate 
essentially from inorganic salts. A suitable base is an aqueous slurry of 
56% solids having sodiumalkyl benzene sulfonate in at least 95% by weight 
of solids. It is convenient to addition of water at this stage to thin the 
mixture to facilitate mixing. The liquid triethanolamine or the like and 
the polyethoxyamer are added in any desired order with stirring. Any 
additional agents are added in powdered or solution form as desired from 
moderate heating, if necessary, to facilitate formation of a homogenous 
solution or dispersion. 
The cleaning solution prepared, as described above, is admixed with the 
zinc sulfate fungicide and the TRITON B-1956 wetting agent-dispersant and 
then diluted with the aqueous solution of acetic acid to produce a 
fungicidal detergent concentrate, as described in Example 1. 
EXAMPLE 3 
This example is further illustrative of the cleaning solutions of the 
present invention. In this example, as set forth below in Table 5 
illustrates a further composition of the cleaning solution. 
TABLE 5 
______________________________________ 
Ingredients Percentage by Weight 
______________________________________ 
Sodium dodecyl sulfonate 
18 
Tridecylpolyeoxyethylene ethanol 
8 
Triethanolamine 10 
TRITON B-1956 wetting agent 
5 
Water and other constituents 
Balance 
______________________________________ 
In the formulation set forth above, the dodecyl benzene sulfonate is 
derived from a propylene tetramer. It is listed in the table on an active 
ingredient basis is substantially free of inorganic salts. The tridecyl 
alcohol is produced by the Oxo process, as previously described, and 
condensed with an average of about 15 moles ethyleneoxide. A solution of 
zinc sulfate in water is mixed into this composition as in Example 1. 
The final formulation is a homogenous, pourable heavy duty liquid at room 
temperature with superior properties. This solution is mixed with the 
dilute solution of acetic acid, as in Example 1, to yield the desired 
cleaning concentrate. 
EXAMPLE 4 
The formulation of Example 3 is repeated except that the following 
approximate proportions are used for the ingredients specified below: 
TABLE 6 
______________________________________ 
Percentage 
Ingredients by Weight 
______________________________________ 
Sodium tridecyl sulfonate 5 
Tridecyl polyethoxyamer (15 moles ethylene 
oxide) 15 
Triethanolamine 10 
TRITON B-1956 wetting agent 
5 
______________________________________ 
This formulation is stable and homogenous at normal room temperature and 
moderately elevated temperatures. This formulation may be mixed with zinc 
sulfate and with the aqueous solution of acetic acid, as described in 
Example 1 above. 
EXAMPLE 5 
A formulation similar to Example 3 is prepared substituting the tridecyl 
(Oxo) polyoxyethylene ethanol having an average of about 10 moles 
ethyleneoxide as the nonionic material. This formulation is satisfactory 
and when mixed with zinc sulfate and aqueous acetic acid produces a 
concentrate which functions substantially the same as that of Example 1. 
EXAMPLE 6 
A cleaning solution is prepared for used in the composition of Example 1 as 
follows: Forty gallons of water is added to a 55-gallon mixing drum. Then, 
33 pounds calcium hypochlorite is mixed in and dissolved. Next, 5 pounds 
Stepan EA-10 nonionic surfactant is dissolved in the solution. Next, 2 
pounds zinc sulfate is dissolved in hot water and added to the solution in 
the drum. Finally, 3 ozs. of TRITON B-1956 wetting agent-dispersant is 
added. The mixture is stirred until completely dissolved and water added 
to fill the drum. 
The solution may be used as is or may be mixed with acetic acid as in 
Example 1. This solution does not require the further dilution with 
aqueous bleach for use. In preparing this cleaning solution, sodium 
hypochorite may be substituted for calcium hypochlorite, or an equivalent 
amount of hydrogen peroxide may be used. 
USE OF CLEANING SOLUTIONS 
To remove mold and mildew from the surface, a concentrate having the 
composition of Example 1 is first mixed with an oxidizing agent such as 
aqueous bleach. As used throughout this specification and claims, the term 
"aqueous bleach" is intended to include ordinary household bleach. For 
best results, the bleach must contain a minimum of 5% wt. sodium 
hypochlorite. The quantities of bleach indicated hereafter are for bleach 
containing 5% wt. sodium hypochlorite. In addition to aqueous bleach, 
peroxide such as sodium peroxide and hydrogen peroxide, and calcium 
hypochlorite may also be employed as the oxidizing agent. 
The zinc sulfate is the primary ingredient responsible for destruction and 
removal of the mold and mildew. The TRITON B-1956 wetting agent assists in 
causing the cleaning solution to wet the surface being cleaned and, when 
dry, resists rewetting and holds enough of the zinc sulfate in place to 
inhibit regrowth of mold and mildew. The oxidizing agent and the acetic 
acid in the concentrate also assist in the removal of mold and mildew. 
Thus, it is usually necessary to add an oxidizing agent, such as bleach, 
to the concentrate immediately prior to treating a surface. The oxidizing 
agent may also be included in the dilute cleaning solution as in Example 
6. 
To treat either exterior wooden surfaces, exterior painted surfaces, metal 
surfaces, plastic surfaces or vinyl surfaces, 1 pt. of the concentrate 
having the composition set forth in Example 1 is mixed with 3 pts. of 
bleach and 2 gals. of water. 
To treat stone, brick, stucco or acoustical tile, 11/2 pts. of the 
concentrate, such as that set forth in Example 1, is mixed with 2 qts. 
bleach and 2 gals. of water. 
For interior surfaces, such as painted walls and ceramic tile, the ratio of 
the concentrate of Example 1 to bleach to water is to 1 to 3 to 26. If the 
mold and mildew detergent composition is to be sprayed from a 1-qt. 
sprayer, the sprayer is loaded with 1 oz. of concentrate, 3 oz. of bleach, 
and 26 oz. of water. If interior walls are to be sprayed from a 4-gal 
sprayer, such a sprayer is loaded with 1 pt. of concentrate, 3 pts. of 
bleach and 3 gals. of water. 
To apply this fungicidal detergent solution, it is convenient to utilize a 
garden sprayer that has been loaded with the correct proportion of 
concentrate, bleach and water. The ingredients may be mixed in the sprayer 
or mixed first in a separate container. In any event, the ingredients 
should be mixed a fairly homogenous system in the sprayer. The mixture in 
the sprayer is then sprayed, preferably as a fine mist over the mildewed 
area. The first coat kills the mold and mildew. A second coat will clean 
the surface, and a third coat will work as a protective coating to inhibit 
regrowth of mold and mildew. The surface may be scrubbed with a brush or 
sponge of the like if desired. 
When successive coats of spray are applied to a surface, it is desirable to 
wait at least five minutes between applications. In most instances, the 
protective coating will prevent the regrowth of mold and mildew for 
periods of up to one to two years. When treating a surface to be painted 
or repainted, it is desirable to rinse the affected area after being 
treated. In this regard, it is recommended to rinse the affected areas 
after treatment only if the surface is going to be painted. After a 
surface has been painted or repained, a protective coating may then be 
applied. To apply such protective coatings to freshly painted surfaces, 
the amount of bleach is reduced to about one-half. Thus, to produce a 
suitable mixture for protecting painted surfaces, one pt. of the 
concentrate of Example 1 is mixed with 11/2 pts. of bleach and 2-3 gals. 
water. 
The fungicidal detergent solution of the present invention is effective in 
removing mold and mildew which may be present on a variety of surfaces, 
such surfaces including stone, brick, stucco, exterior wood, exterior 
painted surfaces, tile, ceramics, metal and plastic materials, automobile 
tires, shower walls, refrigerators and boats. The solution may be applied 
with a large variety of applicators, such applicators including garden 
sprayers, airless paint sprayers, compressor paint sprayers and hand 
sprayers, as well as sponges and brushes. The remover solution not only 
functions as a cleaner to remove the mold and mildew growing on a surface, 
but also protects the treated surface from reoccurrence of mold and mildew 
for extended periods of time. The procedures of application and use of the 
fungicidal detergent concentrate has been described primarily in 
connection with the concentrate set forth in Example 1. The use of the 
concentrates of the other Examples is substantially the same. In addition, 
the solution produced in Example 6 may be used as is or upon further 
dilution as described in that Example. 
While the invention has been described fully and completely with emphasis 
on several preferred embodiments, it should be understood that within the 
scope of the appended claims, the invention may be practiced otherwise 
than as specifically described herein.