CA1156401A - Water repellent aqueous wood treating solutions - Google Patents

Abstract

Abstract of the Disclosure An increased water repellency is imparted to wood and other cellulo-sic natertals with an aqueous solutton containtng a mixture of an aluminum ha1ohydrate and a water soluble salt of a mono, di or trivalent cation select-ed from zinc, manganese, barium, calcium, cobalt, magnesium, nickel, copper, cadmium, strontium, beryllium, lead, mercury, chromium, sodium, lithium, and potassium and a monovalent anion selected from formate acetate, haloacetate, acrylate, methacrylate, propionate, chloro and bromo-propionate, butyrate, isobutyrate, nitrate, sulfamate, iodide, bromide, and chloride, said water soluble salt exc1uding the nitrates, sulfamates, chlorides and bromides of sodium, potassium and lithium.

Description

1 1~6~ ~

WATER REPELLENT AQUEOUS WOOD TREATING SOLUTIONS
S ~r~ e Inventlon This inven~lon relates to s~lutlon~ that provide lncreased water repellen~y for wood and other cellulosic materials. More particularly, the invention is related to aqueous gubgtantially gulfate free cellulo~ic materi-als treating solutions, ~he term solutlon being intended, to include suspen-sions in this context, compris~ng a m~xture of an aluminum halohydrate and a water soluble salt of a mono, di or trivalent cation selected from zinc, manganese, barium, calciumJ cobalt, magnegium, nickel, copper, cadmium, strontium, beryllium, lead, mercury, chromium, sodium, l-lthium, and potassium, and a monovalent anion selected from formate, aceta~e, haloacetate, acrylate, methacrylate, propionate, chloro and bromo-propionate, butyrate, isobutyrate, nitrate, sulfamate, iodide, bromide, and chloride~ said water soluble salt excluding the nitrates, sulfamates, chlorides, and bromides of sodium, potassium, and lithium. The halo and halosubstituted anions can be chloro, bromo, or iodo. The solution can be used to treat paper, cardboard, and cellulosic materials generally, but for convenience, the disclosure describes the treatment of wood.
Aluminum halohy~rates which can be employed include aluminum chloro-hydrate, aluminum iodohydrate, and aluminum bromohydrate.
Exemplary of suitable water soluble salts are:

Zinc Acetate.21120 Zinc Propionate Manganese (+2) Acetate.4H20 Barium Acetate Calcium Acetate : Calcium Iodoacetale Calcium 2-Chloropropionate Calcium 3-Chloropropionate Calcium Isobutyrate Calcium Acrylate Lithiurrl Acetate.21~20 - Calciurn Butyrate ~.

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Il l Calcium Propionate Calcium Forrnate l Cobaltous (~2~ Acetate.4H20 I Magneslum Acetate.4H~0 Nickel (+Z) Acetate.~H20 Cupric Acetate.H~0 Lead (~2) Acetate.3H20 Mercuric (+2) Nitrate, and Il Sodium Acetate.3H20 o ¦ Suitable but somewhat less effective than the preceding are:
Zinc NitrateO6H 0 Magnesium Nitra~e.6H20 Chromic (+3) Acetate~H20 ¦ Cupric Nitrate.3H20 Zinc Chloride Zinc Sulfamate Calcium Chloroacetate l Cadmium Bromide.4H o I Calcium Chloride.2~20 and I Potassium Iodide ¦ Detailed Description of the Invention ¦ The non-aluminum metal salts can be prepared by reacting a mono, di, ¦ or trivalent oxide with the appropriate acid. Thus, zlnc propionate is made ¦ by reacting zinc oxide ~ th propionic acid.
¦ The aluminum halohydrates useful in the invention can be represented I by the Formula: Alx(OH)yXz, wherein X is a halogen such as chlorine, bromine, or iodine and x and y are integers of from 1 to 4 and z is an integer of from 5 to 1. The aluminum halohydrates are usually polymeric in nature and thus ¦ the above formula should not be considered restrict~ve. Typical non-limiting ¦ examples of the aluminum halohydrates that can be used in the present in-¦ vention are: A130H5C14, A140HloC12, A140HgC13~ and A120H4C12. Inasmuch as ¦ sulfate ion will precipitate the aluminum halohydrate, the solution should be substantially free of sulfate.
¦ Any method of treating wood with aqueous treating solutions can be ¦ used when wood is treated w~th the aqueous wood-treating solutions oF the ¦ present invention. These methods include kreating wood by injection of the aqueous wood-treating solution under pressure in closed vessels or dipping in z ~ 1~6~

open vessels or by brush or spr~ painting of the solutiort. Also, in ~he Il method of treating wood with the aqueous ~Jood treating solution of the present ¦l invention, the wood may be end-sealed in any manner known to those skilled lnthe art to enhance the water repellent effect of the aqueous wood-treating solution.
In accordance with -the invention, combination ~ungicide and ~later repellent solu~ions can be made by selecting a fungicide as the water soluble salt. Fun~lcides suitable for use as the water soluble salt can be formed from one of the aforesaid anions and a cation selected from copper, zinc, o barium, lithium, sodium, lead, mercury, cadmium, calcium, and potassium.
Typical fungicides which can be employed as the water soluble salt include:
cadmium formate, cadmium acetate, cadmium propionate, cadmium isobutyrate, cadmium butyrate, cadmium acrylate, cadmium nitrate, cadmium sulfamate, cad-mium chloride, cadmium bromide, cadmium iodide, cadmium iodoacetate, cadmium chloroacetate, cadmium 2-chloropropionate, cadmium 3-chloropropionate, cupric fo~nate, cupric acetate, cupric propionate, cupric isobutyrate, cupric butyr-ate, cupric acrylate, cupric nitrate, cupric sulfamate, cupric chloride, cupric bromlde, cupric iodide, barium formate3 barium acetate, barium propion-ate~ barium isobutyrate, barium butyrate, barium acrylate, barium nitrate, barium sulfamate, barium chloride, barium bromide, barium iodide, barium iodoacetate, barium chloroacetate, barium 2-chloropropionate, barium 3-chloro-propionate, zinc ~ormate, zinc acetate, zinc propionate, zinc isobutyrate, zinc butyrate, zinc acrylate, zinc nitrate, zinc sulfamate, zinc chloride, zinc bromide, zinc iodide, zinc iodoacetate, zinc chloroacetate, zinc

2-chloropropionate, zinc 3-chloropropionate, lithium formate, lithium acetate, lithium propionate, lithium isobutyrate, li-thium butyrate, lithium acrylate, lithium iodide, lithium iodoacetate, lithium chloroacetate, lithium 2-chloro-propionate, lithium 3-chloropropionate, sodium fo~nate, sodium acetate, sodium

-3-llS6401 i~
l l propionate, sodiurn isobutyrate, sq~liulll butyrate, sodium acrylate, sodium iodide, sodiurm iodoacetdte, sodium chloroacetate, sod~um 2-chloropropionate, sodium 3-chloropropionate, potassium fonnate, potassium acetate, potassium propionate, potassium isobutyrate, potdssium butyrate, potassium acrylate, potassium iodide, potassium iodoacetate, potassium chloroacetate, potassium 2 chloropropionate, potassium 3-chloropropiondte, calcium formate, calcium acetate, calcium propionate, calcium lsobutyrate, calcium butyrate, calcium acrylate, calcium iodide, calciuln iodoacetate, calcium chloroacetate, calcium 2-chloropropionate, calcium 3-chloropropionate, mercury (~ 2)acetate or nitrate with aluminum chlorohydrates and lead acetate.
Although the amount of aluminum ha'lohydrate and water soluble salt employed will depend upon the particular materials employed, a treating solu-tion will genera11y contain from about 0.05 to about 2.0~ aluminurn halohydrate and from about 0.06 to about 4.0% water soluble salt. A concentrdte will generally contain either powder or a solution of the more water soluble salts in an amount of from about 5 to 36% aluminum halohydrate and about 10% ~o 18%
water soluble salt.
The following description is directed to several alternative embodi-ments of the aqueous wood-treating solution of the present invention. In these embodiments the alurminum halohydrate used is aluminum chlorohydrate in a 50 percent aqueous solution. Non-lirnitiny examples of such solutions that are commercially available are Wickenol 303 solution, Wickeno'l 305 solution, and Wickenol 306 solution, all available as solu-tions or powders from Wickhen Products, Inc., Hu~uenot, New York. The Wickenol 303 solution is an aqueous 50 percent aluminum chlorohydrate which hds an atomic ratio of two aluminurn atoms to one chlorine atom, Wichenol 305 is the dichlorohydrate and Wickenol 306 the sesquichlorohydrate. Other products which have ratios of one aluminum atom to one chlorine dnd intermediate ratios between one and two aluminum I
* Trade Mark ~ 3 .

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atoms to one ch10rine atom may also be used. The d~luted Wickenol solutions did not appear to exhibit high inherent water repellency when applied to wood by itself, but when used in the aqueous wood-treating solutions of the present invention a synergistic effect is obtained, resulting in an increased w3ter repellency in treated wood.
The following examples will serve to illustrate preferred embodiments of the invention. All parts and percentages in sa1d examples and elsewhere in the specification and claims are by weight unless otherwise specified.

EXAMPLES
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The following stable concentrates which can be diluted to clear solutions were prepared by diluting the ingredients with water before mixing as the use of concentrated solutions tends to inhibit the solubilization of ; the components.

Ingredients Percent by Wei~ht Zinc Propionate 14.0 Zinc Acetate.2H20 --- 20.3 20.3 Wickenol *303 22.5 32.4 ---Wickenol 306 --- --- 32.4 - Deionized Water 63.5 47.3 47.3 Total Weight Percent 100.0 100.0 100.0 *Wickenol is a trade mark for aluminum chlorohydrate.

The above solutions were diluted with water to one percent zinc metal content and tested for inhibition of ceratocystis piliferia (a common sapstain fungus) mixed with mold growth and spores from wet infected pine sapwood.

Small, clear, dry southern pine sapwood specimens were vacuum treated with an aqueous suspension of the mold and sapstain spores to a very high moisture content and cilpped into the above descr1bed ~ilutions. After one week at ro~n temperature and 100 percent relatiYe humldity, the untreated controls were heavily sapstained but none of the treated specimens were attacked. The incubation period was con~inued for a total of three weeks with no sapstain attack on the treated specimens. The test was repeated using the first two solu-tions diluted to a 0.06 percent zinc metal content and there was no evidence of sapstain growth aFter 37 days . A solut~on of zinc acetate, 2H20 alone at 0.21~ had no fungicidal effect against sapstain.
Freshly planed dry southern pine sapwood ~oards containing over 50%
~ springwood on the area to be tested were treated with test solutions by de-¦ positing a few drops of the solution on the wood and spreading with a sponge. The treated boards were dried for 24 hours at ambient temperature and ¦l allowed to sit for a week. The resultant boards were treated with 4 drops of I ~ water on both treated and untreated portions of the boards with a medicine dropper. The number of drops remaining on the boards was recorded after 15 minutes~ 30 minutes, 1 hour, and ~/2hours, as a measure of the board's water ~ repellency. The data obtained is reported in the following table.

; AQUEOUS TREATING SOLUTION NUMBER OF WATER DROPS
REMAINING FROM THE FOUR APPLIED

Wickenols Metal Salt at At 1.6% Soln. 15 30 1 1.5 1.0% B~ Wei~ht ~ PH Min. Min. Hour Hours Barium Acetate None 7.5 0 0 Barium Acetate W-306 5.3 4 4 2 2 Barium Acekate W-303 6.0 4 4 4 2 Barium Acetate W-305 4.9 4 4 4 4 Calcium Acrylate None O O
Calcium Acrylate W-303 5.9 4 4 4 4 Ca Iodoacetate W-303 4.7 4 4 4 3 Ca ~sobutyrate W-303 5.5 4 4 4 3 Ca 2-CL Propionate W-303 5.6 4 4 4 3 Ca 3-CL Propionate W-303 4.6 4 4 4 3 Ca Chloroacetate W-303 4.2 4 4 2 (Table Continued) -6~

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AQUEOUS TREAlING SOLUTION NUMBER OF WATE~ DROPS
REMAINING FRUM THE FOUR APPLIED

Wickenols Metal Salt atAt 1.6% Soln~ 15 30 1 1.5 ~ L~ By Weight PH Min. Min. Hour Hours Zinc Acetate.2H20None 6.9 0 0 Zinc Acetate.2H20W-306 5,3 4 4 3 2 Zinc Acetate.2H20W-303 5.7 4 4 4 3 Zinc Acetate.2H20W-305 5.0 4 4 4 4 Zinc Propionate None 6.2 0 0 Zinc Propionate W-306 5.3 4 4 4 4 Zinc Propionate W-303 5.6 4 4 4 4 Zinc Propionate W 305 5.0 4 4 4 4 Calcium Acetate None 6.7 0 O
I Calcium Acetate W-306 5.5 4 4 4 4 Calcium Acetate W-303 6.1 4 4 4 4 Calcium Acetate W-305 5.1 4 4 4 4 Sodium Acetate.3H20 None 7-9 Sodium Acetate.3H20 W-30S 5.4 4 4 4 4 Sodium Acetate.3H20 W-303 5.5 4 4 4 4 Sodium Acetate.3H O W-305 5.0 4 4 4 4 Lithium Acetate.2~20 W-306 5.5 4 4 4 4 Magnesium Acetate.4H20 W-306 5.6 4 4 4 4 NONE W-303 5.1 4 0 ¦ NONE W-306 4.4 4 0 NONE W-305 4.2 4 0 The following data tends to show a synergistic effect for the two salts. The specimens were tested for water repellancy three weeks after applying the treating solutions.

1 1~6401 ll Number of Dtstilled Water Drops ¦i Weight Percent Metal Welght Percent Remaining From the 4 Applied After Salt in Solutlon Wickenols Used 30 Min. 1 Hour 1.5 Hours 2 Hours 2% Sodium Acetate, 3H20 None o 0 0 1% Sodium Acetate 1.6 W-303 4 4 1 0 2% Barium Acetate None 0 0 0 0 1% Barium Acetate 1.6 W-305 4 4 1 0 2% Zinc Acetate, 2H20 None 4 0 0 l 1% Zinc Acetate, 2H20 1.6 W-303 4 4 4 0 1 2% Zinc Proplonate None 4 0 0 0 1% Zinc Propionate 1.6 W-303 4 4 4 0 1 2% Calcium Formate None 0 0 0 1 1% Calcium Formate 1.6 W-305 4 2 1 0 ¦ 2% Calcium Acetate None 1% Calcium Acetate 1.6 W-303 4 4 3 l None 3.2 W-303 2 1 1 0 I None 3.2 W-306 1 0 0 0 ¦ None 3.2 W-305 0 0 0 ¦ Untreated Wood 0 It was found that high temperature drying of the treated wood de-creases its water repellency, accordingly, temperatures should be kept as low as possible or less than about 160F dry bulb temperature to a moisture con-tent o~ 25%o If clear solutions are desired so that the cellulose product is not discolored, then the copper, nickel and chromium salts should be avoided as these salts discolor the wood whereas the other salts do not.
Further, in formulating barium solutions it was necessary to employ distilled water because the barium salts react with the small amounts o~
sulfate ion found in most tap water.
While the invention has been illustrated by specific examples, the other compounds enumerated in the dlsclosure are found to have water repel-lency effec~iveness when used to treat cellulosic materials, and may have fungic~dal effec veness.

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An aqueous, substantially sulfate free, cellulosic material treating solutlon that provides an increased water repellency, consisting essentially of an alumlnum halohydrate wherein the halogen 15 selected from chlorine, bromine and iodine and a water soluble salt of a mono, di or trivalent cation selected from zinc, manganese, barium, calcium, cobalt, magnesium, nickel, copper, cadmium, strontlum, beryllium, lead, mercury, chromium, sodium, lithium, and potassium and a monovalent anion selected from formate, acetate, haloacetate, acrylate, methacrylate, propionate, chloro and bromo-propionate, butyrate, isobutyrate, nitrate, sulfamate, iodide, bromide, and chloride, said water soluble salt excluding the nitrates, sulfa-mates, chlorides and bromldes of sodlum, potassium and lithium.

2. The solution of Claim 1 wherein the aluminum halohydrdte is aluminum chlorohydrate and the water soluble salt is selected from:
Zinc Acetate Zinc Propionate Manganese Acetate Barium Acetate Calcium Acetate Calcium Iodoacetate Calcium 2-Chloropropionate Calcium 3-Chloropriopionate Calcium Isobutyrate Calcium Acrylate Calcium Butyrate Calcium Propionate Calcium Formate Cobalt Acetate Magnesium Acetate Nickel Acetate Cupric Acetate Lithium Acetate Lead Acetate Mercury Nitrate and mixtures

3. The solution of Claim 1 wherein the aluminum halohydrate is aluminum chlorohydrate and the water soluble sat is selected from:
Zinc Nitrate Magnesium Nitrate Chromium Acetate Cupric Nitrate Zinc Chloride Zinc Sulfamate Sodium Acetate Calcium Chloride Potassium Iodicle Calcium Chloroacetate Cadmium Bromide and mixtures

4. The solution of Claim 1 wherein the alumlnum halohydrate is present in an amount of between about 0.05 and about 2.0 parts by weight of the solution.

5. The solution of Claim 1 wherein the water soluble salt is present in an amount of from between about 0.06 and about 4.0 by weight of the solution.

6. The solution of Claim 1 wherein the aluminum halohydrate is aluminum chlorohydrate.

7. A substantially sulfate free water repellent concentrate for aqueous dilution to form a cellulosic material treating solution, that provides an increased water repellency consisting essentially of from about 5%

to about 36% by weight of an alumlnum halohydrate wherein the halogen is selected from chlorlne, bromine, and iodine and from about 10% to about 15 by weight of a water soluble salt of a mono, di or trivalent cation selected from zlnc, manganese, barium, calcium, cobalt, magnesium, nickel, copper, cadmium, strontium, beryllium, lead, mercury, chromium, sodium, lithium, and potassium and a monovalent anion selected from fonnate, acetate, haloacetate, acrylate, methacrylate, propionate, chloro and bromo-propionate, butyrate, isobutyrate, nitrate, sulfamate, iodide, bromide, and chloride, said water soluble salt excluding the nitrates, sulfamates, chlorides and bromides of sodium, potassium and lithium.

8. The concentrate of claim 7 whereon the aluminum halohydrate is present in an amount from about 5% to about 36% by weight and the water soluble salt is present in an amount from about 10% to about 18%.

9. A method for increaslng the water repellency of cellulosic materials comprising treating the cellulosic materials with an aqueous solu-tion consisting essentially of an effective amount of a mixture of aluminum halohydrate wheréin the halogen is selected from chlorine, bromine, and iodine and a water soluble salt of a mono, di or trivalent cation selected from zinc, manganese, barium, calcium, cobalt, magnesium, nickel, copper, cadmium, strontium, beryllium, lead, mercury, chromium, sodium, lithium, and potassium and a monovalent anion selected from formate, acetate, haloacetate, acrylate, methacrylate, propionate, chloro and bromo propionate, butyrate, isobutyrate, nitrate, sulfamate, ioclide, bromide, and chloride, said water soluble salt excluding the nitrates, sulfamates, chlorides and bromides of sodium, potassium and lithium.

10. A substantially sulfate free fungicidal concentrate for aqueous dilution to form a fungicide consisting essentially of all aluminum halo-hydrate wherein the halogen is selected from chlorine, bromine and iodine and a water soluble salt of a mono or divalent cation selected from copper, zinc, barium, lithium, lead, mercury, cadmium, calcium, sodium, and potassium, and a monovalent anion selected from formate, acetate, haloacetate, acrylate, methacrylate, propionate, chloro and bromo-propionate, butyrate, isobutyrdte, nitrate, sulfamate, iodide, bromide, and chloride, said water so1uble salt excluding the sulfamates, nitates, chlorides and bromides of sodium, potassium, lithium and calcium.

11. The concentrate of claim 10 wherein the aluminum halohydrate is present in an amount from about 5% to about 36% by weight and the water solu-ble salt is present in an amount from about 10% to about 18% by weight.

12. A method for controlling fungi consisting essentially of treat-ing said fungi with a fungicidal amount of an aluminum halohydrate wherein the halogen is selected from chlorine, bromine and iodine and a water soluble salt of d mono or divalent cation selected from copper, zinc, barium, lithium, lead, mercury, cadmiuln, calcium, sodium, and potassium, and a mono-valent anion se1ected from formate, acetate, haloacetate, acrylate, methacry-late, propionate. chloro and bromo-propionate, butyrate, isobutyrate, nitrate, sulfamate, iodide, bromide, and chloride, said water soluble salt excluding the sulfamates, nitrates, chlorides and bromides of sodium, potassium, lithium and calcium.

13. A concentrate of Claim 10 wherein the aluminum halohydrate is aluminum chlorohydrate and the water soluble salt is selected from cadmium formate, cadmium acetate, cadmium propionate, cadmium isobutyrate, cadmium butyrate, cadmium acrylate, cadmium nitrate, cadmium sulfamate, cadmium chlor-ide, cadmium bromide, cadmium iodide, cadmium iodoacetate, cadmium chloroace-tate, cadmium 2-chloropropionate, cadmium 3-chloropropionate, cupric formate, cupric acetate, cupric propionate, cupric isobutyrate, cupric butyrate, cupric acrylate, cupric nitrate, cupric sulfamate, cupric chloride, cupric bromide, cupric iodide, barium formate, barium acetate, barium propionate, barium isobutyrate, barium butyrate, barium acrylate, barium nitrate, barium sulfa-mate, barium chloride, barium bromide, barium iodide, barium iodoacetate, barium chloroacetate, barium 2-chloropropionate, barium 3-chloropropionate, zinc formate, zinc acetate, zinc propionate, zinc isobutyrate, zinc butyrate, zinc acrylate, zinc nitrate, zinc sulfamate, zinc chloride, zinc bromide, zinc iodide, zinc iodoacetate, zinc chloroacetate, zinc 2-chloropropionate, zinc 3-chloropropionate, lithium formate, lithium acetate, lithium propionate, lithium isobutyrate, lithium butyrate, lithium acrylate, lithium iodide, lithium iodoacetate, lithium chloroacetate, lithium 2-chloropropionate, lithium 3-chloropropionate, sodium formate, sodium acetate, sodium propionate, sodium isobutyrate, sodium butyrate, sodium acrylate, sodium iodide, sodium iodoacetate, sodium chloroacetate, sodium 2-chloropropionate, sodium 3-chloro-propionate, potassium formate, potassium acetate, potassium propionate, potas-sium isobutyrate, potassium butyrate, potassium acrylate, potassium iodide, potassium iodoacetate, potassium chloroacetate, potassium 2-chloropropionate, potassium 3-chloropropionate, calcium formate, calcium acetate, ca1cium pro-pionate, calcium isobutyrate, calcium butyrate, calcium acrylate, calcium iodide, calcium iodoacetate, calcium chloroacetate, calcium 2-chloropropion-ate, calcium 3-chloropropionate, mercury (+2) acetate or nitrate with aluminum chlorohydrates and lead acetate.

14. A method for increasing the water repellency of wood consisting essentially of treating the wood with an aqueous solution comprising an effec-tive amount of a mixture of aluminum halohydrate wherein the halogen is selected from chlorine, bromine and iodine and a water soluble salt of a mono, di or trivalent cation selected from zinc, manganese, barium, calcium, cobalt, magnesium, nickel, copper, cadmium, strontium, beryllium, lead, mer-cury, chromium, sodium, lithium, and potassium and a monovalent anion selected from fonmate, acetate, haloacetate, acrylate, methacrylate, propionate, chloro and bromo-propionate, butyrate, isobutyrate, nitrate, sulfamate, iodide, bromide, and chloride, said water soluble salt excluding the nitrates, sulfa-mates, chlorides and bromides of sodium, potassium and lithium.

15. A method for increasing the water repellency of cellulosic materials and for controlling fungi consisting essentially of treating said materials and fungi with an effective amount of aluminum halo hydrate wherein the halogen is selected from chlorine, bromine and iodine and a water soluble salt of a mono or divalent cation selected from copper, zinc, barium, lithium, lead, mercury, cadmium, calcium, sodium, and potassium, and a mono-valent anion selected from formate, acetate, haloacetate, acrylate, methacrylate, propionate, chloro and bromo-propionate, butyrate, isobutyrate, nitrate, sulfamate, iodide, bromide, and chloride, said water soluble salt excluding the sulfamates, nitrates, chlorides and bromides of sodium, potassium, lithium and calcium.