A novel composition of matter comprising a color-inhibiting additive, such as sodium bisulfite, and cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride or the cis-, trans- mixtures of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, is a non-yellowing antimicrobial formulation suitable for the preservation of aqueous organic mixtures such as emulsions, dispersions, latexes and solutions. The color-inhibiting agent may be added as a solid or as an aqueous solution wherein the weight ratio of adamantane to additive is from about 1:0.01 to about 1:4.

BACKGROUND OF THE INVENTION 
Products prepared by reacting hexamethylenetetramine with 
1,3-dichloropropene are well-known and successful antimicrobial agents; 
U.S. Pat. No. 3,228,829. One product, 
cis-1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, 
commercially available as DOWICIL.RTM. (Registered trademark of The Dow 
Chemical Company) 200 and hereinafter referred to as "cis-compound" is 
used primarily in cosmetic and allied formulations. Another product, 
cis-,trans- mixtures of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane 
chloride, commercially available under the DOWICIL.RTM. tradename, 
containing from about 50 to 99.5 percent cis-isomer and about 50 to 0.5 
percent trans-isomer, is hereinafter referred to as "cis-,trans-compound". 
The cis-,trans-compound is used in commercial formulations such as, 
emulsifiable metal-cutting fluids; latex and emulsion paints; liquid floor 
polishes and floor waxes; glues and adhesives; coatings, sizings and 
printing colors for pulp and paper; and finishing solutions and printing 
pastes used by textile producers. 
Although well-known and successful as anti-microbial agents, the cis- and 
cis-,trans-compounds may cause yellowing of the treated formulations. This 
yellowing seems to occur quickly, requiring only a few days to develop. 
Certain amine compounds were found to inhibit color formation in aqueous 
solutions containing the cis- and cis-,trans-compounds. Polemenakos and 
Langer in U.S. Pat. No. 3,908,009 teach the use of amine compounds to 
stabilize solutions against discoloration. However it was found that the 
amines that work well in aqueous solutions did not work in the latex 
systems. It is desirable to prevent the yellowing of most compositions 
containing the aforesaid antimicrobial agents, especially in areas such as 
the latex and cosmetic industries. 
This invention provides a novel composition of matter which utilizes the 
effective antimicrobial properties of the cis-compound and 
cis-,trans-compound and affords a non-yellowing formulation. 
SUMMARY OF THE INVENTION 
A novel composition of matter consisting essentially of cis- or 
cis-,trans-compound and a color-stabilizing agent, such as sodium 
bisulfite, is useful as a non-yellowing, antimicrobial agent in aqueous 
dispersions, solutions, etc. which are subject to attack by putrefactive 
bacteria. The non-yellowing, antimicrobial agent of this invention, is 
especially useful in the cosmetic and latex industries and prevents the 
loss of useful properties, foul odors, slime formation, and the 
possibility of skin infections in persons handling aqueous systems 
preserved against microbial decomposition. 
The color-stabilizing additive is a reducing agent selected from alkali 
metal, alkaline earth metal, amine or ammonium sulfites or bisulfites; 
inorganic hydrides; or hydroxylamine and acid salts thereof. The additives 
may be added as a solid or as an aqueous solution. The preferred weight 
ratio of cis- or cis-,trans-compound to additive is from about 1:0.01 to 
about 1:4. 
DETAILED DESCRIPTION OF THE INVENTION 
A color-stabilizing additive in combination with a cis-compound or a 
cis-,trans-compound forms a novel composition of matter having 
non-yellowing, antimicrobial properties. 
In making cis-,trans-compound, the hexamethylenetetramine is reacted with a 
commercial mixture containing cis- and trans-1,3-dichloropropene and inert 
material. While in the case of cis-compound, the cis-1,3-dichloropropene 
is separated from the above mixture and reacted with 
hexamethylenetetramine to give cis-compound. A method for the preparation 
of this cis-compound and the cis-,trans-compound is found in U.S. Pat. No. 
3,228,829 and is incorporated herein by reference. 
Compounds from the known class of reducing agents are particularly suitable 
color-stabilizing additives in the instant invention. 
The reducing agent may be selected from alkali metal, alkaline earth metal, 
amine or ammonium sulfites or bisulfites; inorganic hydrides; or 
hydroxylamine and acid salts thereof. Following are more compounds which 
are illustrative reducing agents: sodium sulfite, sodium bisulfite, 
potassium sulfite, potassium bisulfite, lithium sulfite, lithium 
bisulfite, magnesium sulfite, magnesium bisulfite, calcium bisulfite, 
ammonium sulfite, ammonium bisulfite, sodium borohydride, lithium aluminum 
hydride, lithium borohydride, hydroxylamine hydrochloride, hydroxylamine, 
hydroxylamine sulfate and the like. The preferred color-inhibiting 
additives are sodium sulfite, sodium borohydride, sodium bisulfite, and 
hydroxylamine hydrochloride. 
The color-stabilizing additive or reducing agent may be added as a solid or 
as an aqueous solution. The additive may also comprise a mixture of the 
suitable reducing agents. The preferred weight ratio of cis- or 
cis-,trans-compound to additive is from about 1:0.01 to about 1:4, most 
preferably 1:1. Generally a 1:1 (additive/cis-compound) weight ratio is 
required for inhibiting discoloration of compositions containing 
cis-compound using hydroxylamine hydrochloride and sodium bisulfite. 
Greater ratios can be used if desired. Lower ratios may be effective 
depending on the system used. The amount of NaBH.sub.4 needed to control 
color formation was found to be much smaller. For example a 1:10 
(additive/cis-compound) weight ratio was found to be sufficient for color 
stabilization. Larger amounts of NaBH.sub.4 can also be used. 
In the preparation of the novel composition of matter of this invention, 
the color-stabilizing additive may be incorporated into the cis-compound 
or cis-,-trans-compound by any conventional means suitable for mixing 
powders, including stirring, blending, use of a mortar and pestle, etc. 
Advantageously, the color-stabilizing additive is added to an aqueous 
solution or formulation as soon as it is made, and, for best results, as 
soon as possible after the antimicrobial, cis- or cis-,trans-compounds are 
added to the water-containing formulation. In the aforesaid manner, the 
novel composition of matter of this invention is generated in situ. If 
desired, the aqueous phase may be buffered to an appropriate pH, e.g., 
between 6 and 8. However, buffering is not essential to the successful use 
of the novel composition of this invention. 
Both cis-compound and cis-,trans-compound containing a color-stabilizing 
additive may be used in clear or light-colored formulations containing a 
continuous or discontinuous aqueous phase wherein the antimicrobial is 
present primarily in the aqueous phase. The color stabilizing additive is 
used to prevent undesirable yellowing on aging. The amount of cis- or 
cis-,trans-compound used as a preservative may vary from 0.01 to about 20 
weight percent based on the total weight of the water-containing 
formulation. Formulations which are known to benefit from the use of 
antimicrobial agents are emulsifiable metal-cutting fluids; latex and 
emulsion paints; liquid floor polishes and floor waxes; glues and 
adhesives; coatings, sizings and printing colors for pulp and paper; 
finishing solutions and printing pastes used by textile producers; and 
cosmetics. In practice, the stabilized compositions of the present 
invention are prepared by merely adding the color-stabilizing additive to 
the cis- or cis-,trans-compound formulation in the amounts indicated above 
and mixing thoroughly by conventional means. 
Generally, the conditions for mixing the novel composition of matter of 
this invention and aqueous industrial formulations are not temperature or 
pressure sensitive and room temperatures (i.e., 20.degree. C. to 
25.degree. C.) and atmospheric or superatmospheric pressures may be used 
as a matter of convenience.

The following non-limiting examples clearly illustrate the invention. 
Unless otherwise specified, parts and percentages are by weight. 
EXAMPLE 1 
In a glass vessel, at 22.degree. C. an aqueous solution of cis-compound (1 
percent by weight) is prepared. The solution is subjected to accelerated 
aging by placing the vessel containing the solution in a 54.degree. C. 
water bath. A comparison of yellowing results between cis-compound 
solutions at ambient temperature (i.e., 20.degree. C.-25.degree. C.) and 
54.degree. C. resulted in an approximate aging relationship of 24 hours at 
54.degree. C. being equivalent to three weeks at ambient temperature. 
After 72 hours at 54.degree. C. (9 weeks of aging), the color of the 
solution was intensely yellow, having increased from a Gardner color of &lt;1 
to about 7. The Gardner color is obtained by matching the color of the 
sample with the appropriate standard tube. Tube numbers 1-8 are based on 
solutions of potassium chloroplatinate while tube numbers 9-18 are based 
on solutions of ferric chloride and cobalt chloride. See ASTM Method 
D1544-58I. The instant example clearly illustrates the intense yellowing 
that occurs on the aging of an aqueous solution of the cis-compound. 
EXAMPLES 2-3 
Under similar conditions described in Example 1, cis-compound and an 
additive are dissolved in water in the quantities shown below. The 
aqueous, cis-compound/additive solution is aged at 54.degree. C. in a 
water bath. In Table I, the results using two color-inhibiting additives 
are summarized after 72 hours (9 weeks aging). 
TABLE I 
______________________________________ 
Non-Yellowing Aqueous Compositions 
Gardner - Ex. *Amt. of *Amt. of Color 
2 
No. Additive Additive Cis-Compound 
Before 
After 
______________________________________ 
2 Sodium 1% 1% &lt;1 &lt;1 
borohydride 
3 Hydroxyl- 1% 1% &lt;1 &lt;1 
amine 
hydro- 
chloride 
______________________________________ 
*Weight percent is based on the total weight of the system. 
EXAMPLE 4 
Two separate aqueous solutions are prepared as described in Example 1. One 
solution contained 2 percent cis-compound and 2 percent sodium bisulfite. 
The other solution contained 2 percent cis-compound and is used as a 
control. Both solutions are aged at 54.degree. C. for 144 hours (18 
weeks). The initial pH is adjusted to 10.0 for both solutions. The 
comparison shown in Table II below illustrates the effectiveness of the 
sodium bisulfite (NaHSO.sub.3) additive in preventing the yellowing of the 
aqueous solution. 
TABLE II 
______________________________________ 
Effect of NaHSO.sub.3 on Yellowing of 
Aqueous Solution 
Gardner Color 
Additive Before After 
______________________________________ 
none &lt;1 .about.7 (intense yellow) 
sodium bisulfite 
&lt;1 .about.2 (faint yellow) 
______________________________________ 
EXAMPLES 5-6 
Aging Study of Latex Systems (75 Percent Vinyl Acetate/25 Percent Butyl 
Acrylate) 
A latex system is prepared by diluting a vinyl acetate/butyl acrylate latex 
1:1 with deionized water and adding cis-compound (0.1 weight percent based 
on latex) and a specified additive. Samples were aged at 54.degree. C. for 
three weeks and at 75.degree. C. for ten days. The Gardner color standards 
were not used to monitor the discoloration of the latex systems. A rating 
of 0-5 was chosen wherein 0 represents white and 5 represents a complete 
change in hue. This method was found to relate more accurately the color 
changes that occur in the latex systems. Results of the aging studies are 
shown in Tables III and IV. 
TABLE III 
______________________________________ 
Aging Study of Latex System - 54.degree. C. 
Color- 
Stabilizing 
Color 
System Additive* Before After 
______________________________________ 
latex 0 0 
latex + Cis-Compound 0 2 
latex + Cis-Compound + 
NaBH.sub.4 0 0 
latex + Cis-Compound + 
NH.sub.2 OH . HCl 
0 0 
latex + NH.sub.4 OH 0 3 
+ Cis-Compound 
latex + NH.sub.4 OH 
+ Cis-Compound + NaBH.sub.4 0 0 
______________________________________ 
*Color-stabilizing additives are 0.1 weight percent based on latex. 
**The latex as produced is acidic, but users will normally pH adjust the 
finished paint to a pH of 8.5-9.0 with an amine such as ammonia. 
TABLE IV 
______________________________________ 
Aging Study of Latex System - 75.degree. C. 
Color- 
Stabilizing Color 
System Additive** Before After 
______________________________________ 
latex + NH.sub.4 OH* 0 2 
latex + NH.sub.4 OH 
+ Cis-Compound 0 5 
latex + NH.sub.4 OH 
+ Cis-Compound + 
NH.sub.2 OH . HCl (0.1%) 
0 0 
latex + NH.sub.4 OH 
+Cis-Compound + 
NaBH.sub.4 (0.05%) 
0 0 
latex + NH.sub.4 OH 
+ Cis-Compound + 
NaBH.sub.4 (0.1%) 
0 0 
latex + NH.sub.4 OH 
+ Cis-Compound + 
NaHSO.sub.3 (0.1%) 
0 2 
latex + NH.sub.4 OH 
+ Cis-Compound + 
NaHSO.sub.3 (0.5%) 
0 1 
______________________________________ 
*The latex as produced is acidic, but users will normally pH adjust the 
finished paint to a pH of 8.5-9.0 with an amine such as ammonia. 
**Color-stabilizing additives are expressed as weight percentages based o 
the latex. 
EXAMPLE 7 
In this example, yellowing is monitored for amine/cis-compound stabilized 
latex solutions and aqueous solutions. 
The Gardner standards were used to determine the color of the aqueous 
solutions while the method described in Examples 5-6 is used to monitor 
discoloration in the latex systems. The aqueous solutions consist of 1 
percent cis-compound and 1 percent amine based on the total weight of the 
solution. The latex systems consist of 0.1 percent cis-compound and 0.1 
percent amine based on the weight of the latex. 
The aqueous solutions were aged for 72 hours at 54.degree. C. (9 weeks at 
room temperature). The latex solutions were aged for three weeks at 
54.degree. C. 
TABLE V 
______________________________________ 
Amine Inhibited Yellowing Study 
Color 
Aqueous System Before After 
______________________________________ 
Cis-Compound in water &lt;1 7 
Cis-Compound + diethanolamine in water 
&lt;1 &lt;1 
Cis-Compound + 1,3-propanediamine in water 
&lt;1 &lt;1 
Cis-Compound + 1,2-propanediamine in water 
&lt;1 &lt;1 
Color 
Latex System Before After 
______________________________________ 
latex + Cis-Compound 0 2 
latex + Cis-Compound 
+ diethanolamine in water 
0 3 
latex + Cis-Compound 
+ 1,3-propanediamine in water 
0 5 
latex + Cis-Compound 
+ 1,2-propanediamine in water 
0 5 
______________________________________ 
*Gardner color? 
**Color based on 0=white and 5=complete change in hue. 
The above data reveal that certain amine compounds work well in aqueous 
solutions but do not work in the latex systems.