Abstract:
An increased water repellency is imparted to wood and other cellulosic materials with an aqueous solution containing a mixture of an aluminum halohydrate 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, iodide, bromide, and chloride, said water soluble salt excluding the nitrates, sulfamates, chlorides and bromides of sodium, potassium and lithium.

Description:
This is a continuation of application Ser. No. 096,333, filed Nov. 21, 1979, now abandoned. 
    
    
     SUMMARY OF THE INVENTION 
     This invention relates to solutions that provide increased water repellency for wood and other cellulosic materials. More particularly, the invention is related to aqueous substantially sulfate free cellulosic materials treating solutions to include suspensions, comprising a mixture of an aluminum halohydrate 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 bromopropionate, 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 halohydrates which can be employed include aluminum chlorohydrate, aluminum iodohydrate, and aluminum bromohydrate. 
     Exemplary of suitable water soluble salts are: 
     Zinc Acetate.2H 2  O 
     Zinc Propionate 
     Manganese (+2) Acetate.4H 2  O 
     Barium Acetate 
     Calcium Acetate 
     Calcium Iodoacetale 
     Calcium 2-Chloropropionate 
     Calcium 3-Chloropropionate 
     Calcium Isobutyrate 
     Calcium Acrylate 
     Lithium Acetate.2H 2  O 
     Calcium Butyrate 
     Calcium Propionate 
     Calcium Formate 
     Cobaltous (+2) Acetate.4H 2  O 
     Magnesium Acetate.4H 2  O 
     Nickel (+2) Acetate.4H 2  O 
     Cupric Acetate.H 2  O 
     Lead (+2) Acetate.3H 2  O 
     Mercuric (+2) Nitrate, and 
     Sodium Acetate.3H 2  O 
     Suitable but somewhat less effective than the preceding are: 
     Zinc Nitrate.6H 2  O 
     Magnesium Nitrate.6H 2  O 
     Chromic (+3) Acetate.H 2  O 
     Cupric Nitrate.3H 2  O 
     Zinc Chloride 
     Zinc Sulfamate 
     Calcium Chloroacetate 
     Cadmium Bromide.4H 2  O 
     Calcium Chloride.2H 2  O and 
     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, zinc propionate is made by reacting zinc oxide with propionic acid. 
     The aluminum halohydrates useful in the invention can be represented by the formula: Al x  (OH) y  X z , 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 restrictive. Typical non-limiting examples of the aluminum halohydrates that can be used in the present invention are: Al 3  OH 5  Cl 4 , Al 4  OH 10  Cl 2 , Al 4  OH 9  Cl 3 , and Al 2  OH 4  Cl 2 . 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 with the aqueous wood-treating solutions of the present invention. These methods include treating wood by injection of the aqueous wood-treating solution under pressure in closed vessels or dipping in open vessels or by brush or spray painting of the solution. Also, in the method of treating wood with the aqueous wood treating solution of the present invention, the wood may be end-sealed in any manner known to those skilled in the art to enhance the water repellent effect of the aqueous wood-treating solution. 
     In accordance with the invention, combination fungicide and water repellent solutions can be made by selecting a fungicide as the water soluble salt. Fungicides suitable for use as the water soluble salt can be formed from one of the aforesaid anions and a cation selected from copper, zinc, 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, cadmium chloride, cadmium bromide, cadmium iodide, cadmium iodacetate, cadmium chloroacetate, 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 sulfamate, 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-chloropropionate, potassium formate, potassium acetate, potassium propionate, potassium isobutyrate, potassium butyrate, potassium acrylate, potassium iodide, potassium iodoacetate, potassium chloroacetate, potassium 2-chloropropionate, potassium 3-chloropropionate, calcium formate, calcium acetate, calcium propionate, calcium isobutyrate, calcium butyrate, calcium acrylate, calcium iodide, calcium 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 halohydrate and water soluble salt employed will depend upon the particular materials employed, a treating solution will generally contain from about 0.05 to about 2.0% aluminum halohydrate and from about 0.06 to about 4.0% water soluble salt. A concentrate 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% to 18% water soluble salt. 
     The following description is directed to several alternative embodiments of the aqueous wood-treating solution of the present invention. In these embodiments the aluminum halohydrate used is aluminum chlorohydrate in a 50 percent aqueous solution. Non-limiting examples of such solutions that are commercially available are Wickenol 303 solution, Wickenol 305 solution, and Wickenol 306 solution, all available as solutions or powders from Wickhen Products, Inc., Huguenot, New York. The Wickenol 303 solution is an aqueous 50 percent aluminum chlorohydrate which has an atomic ratio of two aluminum atoms to one chlorine atom, Wichenol 305 is the dichlorohydrate and Wickenol 306 the sesquichlorohydrate. For non-drug use, Wickenol 303 is now known as Wicklor 904--Al complex 56, Wicklor 305 is now known as Wicklor 906--Al complex 23, and Wickenol 306 is now known as Wicklor 905--Al complex 34. Other products which have ratios of one aluminum atom to one chlorine and intermediate ratios between one and two aluminum atoms to one chlorine atom may also be used. The diluted 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 water repellency in treated wood. 
    
    
     The following examples will serve to illustrate preferred embodiments of the invention. All parts and percentages in said examples and elsewhere in the specification and claims are by weight unless otherwise specified. 
     EXAMPLES 
     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 Weight______________________________________Zinc Propionate          14.0      --        --Zinc Acetate . 2H.sub.2 O          --        20.3      20.3Wickenol 303*  22.5      32.4      --Wickenol 306   --        --        32.4Deionized Water          63.5      47.3      47.3Total Weight Percent          100.0     100.0     100.0______________________________________ *Wickenol is a trade name 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 dipped into the above described dilutions. After one week at room temperature and 100 percent relative humidity, the untreated controls were heavily sapstained but none of the treated specimens were attacked. The incubation period was continued for a total of three weeks with no sapstain attack on the treated specimens. The test was repeated using the first two solutions diluted to a 0.06 percent zinc metal content and there was no evidence of sapstain growth after 37 days. A solution of zinc acetate, 2H 2  O alone at 0.21% had no fungicidal effect against sapstain. 
     Freshly planed dry southern pine sapwood boards containing over 50% springwood on the area to be tested were treated with test solutions by depositing 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 allowed to sit for a week. The resultant boards were treated with 4 drops of 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 11/2 hours, as a measure of the board&#39;s water repellency. The data obtained is reported in the following table. 
     
         ______________________________________AQUEOUS TREATINGSOLUTION      Wick-        NUMBER OF WATER      enols        DROPS REMAINING      At           FROM THE FOUR      1.6%         APPLIEDMetal Salt at        By      Soln.  15   30   1    1.51.0% By Weight        Weight  PH     Min. Min. Hour Hours______________________________________Barium Acetate        None    7.5    0    0Barium Acetate        W-306   5.3    4    4    2    2Barium Acetate        W-303   6.0    4    4    4    2Barium Acetate        W-305   4.9    4    4    4    4Calcium Acrylate        None           0    0Calcium Acrylate        W-303   5.9    4    4    4    4Ca Iodoacetate        W-303   4.7    4    4    4    3Ca Isobutyrate        W-303   5.5    4    4    4    3Ca 2-CL Propionate        W-303   5.6    4    4    4    3Ca 3-CL Propionate        W-303   4.6    4    4    4    3Ca Chloroacetate        W-303   4.2    4    4    2    1Zinc Acetate.2H.sub.2 O        None    6.9    0    0Zinc Acetate.2H.sub.2 O        W-306   5.3    4    4    3    2Zinc Acetate.2H.sub.2 O        W-303   5.7    4    4    4    3Zinc Acetate.2H.sub.2 O        W-305   5.0    4    4    4    4Zinc Propionate        None    6.2    0    0Zinc Propionate        W-306   5.3    4    4    4    4Zinc Propionate        W-303   5.6    4    4    4    4Zinc Propionate        W-305   5.0    4    4    4    4Calcium Acetate        None    6.7    0    0Calcium Acetate        W-306   5.5    4    4    4    4Calcium Acetate        W-303   6.1    4    4    4    4Calcium Acetate        W-305   5.1    4    4    4    4Sodium Acetate.3H.sub.2 O        None    7.9    0    0Sodium Acetate.3H.sub.2 O        W-306   5.4    4    4    4    4Sodium Acetate.3H.sub.2 O        W-303   5.5    4    4    4    4Sodium Acetate.3H.sub.2 O        W-305   5.0    4    4    4    4Lithium Acetate.2H.sub.2 O        W-306   5.5    4    4    4    4MagesiumAcetate.4H.sub.2 O        W-306   5.6    4    4    4    4NONE         W-303   5.1    4    0NONE         W-306   4.4    4    0NONE         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. 
     
         ______________________________________              Number of Distilled Water      Weight  Drops Remaining From the      Percent 4 Applied AfterWeight Percent Metal        Wickenols 30     1    1.5   2Salt in Solution        Used      Min.   Hour Hours Hours______________________________________2% Sodium Acetate,        None      0      0    03H.sub.2 O1% Sodium Acetate        1.6 W-303 4      4    1     02% Barium Acetate        None      0      0    0     01% Barium Acetate        1.6 W-305 4      4    1     02% Zinc Acetate,        None      4      0    0     02H.sub.2 O1% Zinc Acetate,        1.6 W-303 4      4    4     02H.sub.2 O2% Zinc Propionate        None      4      0    0     01% Zinc Propionate        1.6 W-303 4      4    4     02% Calcium Formate        None      0      0    01% Calcium Formate        1.6 W-305 4      2    1     02% Calcium Acetate        None      0      0    01% Calcium Acetate        1.6 W-303 4      4    3     1None         3.2 W-303 2      1    1     0None         3.2 W-306 1      0    0     0None         3.2 W-305 0      0    0Untreated Wood         0______________________________________ 
    
     It was found that high temperature drying of the treated wood decreases its water repellency, accordingly, temperatures should be kept as low as possible or less than about 160° F. dry bulb temperature to a moisture content of 25%. 
     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 of sulfate ion found in most tap water. 
     While the invention has been illustrated by specific examples, the other compounds enumerated in the disclosure are found to have water repellency effectiveness when used to treat cellulosic materials, and may have fungicidal effectiveness.