MXPA97008754A - Compositions of chloroisocianuric acid which has reduced reduction of - Google Patents

Abstract

Disclosed are trichloroisocyanuric acid compositions having improved algicidal and / or fungicidal properties, which are relatively safe and non-corrosive. The compositions preferably contain between about 50% and about 95% of TCCA, between about 0.5% and about 7% of glycoluril, between about 2% and about 40% of alum, and between about 40% of borax. The compositions generate substantially less chlorine gas than would be expected from the teachings of the prior art, especially when wet. The compositions of the invention are therefore less toxic and less corrosive

Description

COMPOSITION OF CHLOROISOCYANURIC ACID THAT HAS REDUCED GAS DEPENDMENT FIELD OF THE INVENTION The present invention relates generally to sanitizing tablets for use in water systems, and more particularly to sanitization tablets of chloroisocyanuric acid which are safer and easier to use due to their reduced propensity to generate chlorine gas, dangerous and corrosive.

BACKGROUND OF THE INVENTION Chloroisocyanuric acids such as trichloroisocyanuric acid ("TCCA") have been widely used as sanitizers for water systems such as swimming pools, mineral water spas, etc. One drawback to this use, however, is that chloroisocyanuric acids generate chlorine and chlorine-containing gases that are hazardous to human health and corrosive to water treatment equipment. Corrosive chlorine gas also adversely affects the packaging used to store chloroisocyanuric acid, so that the problems of REF: 26123 Storage associated with the decomposition of the sanitizer are composed of storage problems associated with the corrosion of the packaging itself. The evolution of chlorine gas from the compositions containing TCCA is especially pronounced when the TCCA is wet, such as when the TCCA is formulated in disks or tablets that are placed in the water to sanitize the system. For example, in swimming pools it is common to use systems that supply chemical products that are based on pumps, to recirculate the treated water throughout the system. In many cases, the pump is turned off at night, and when the operator opens the feeder in the morning the initial shock of the chlorine formed can be strong enough to leave the operator sick or disoriented. These problems are well known in the pool chemicals industry, and sanitizers that have a low level of chlorine gas release have been sought to a large extent. It is also known that boron derivatives such as sodium tetraborate (borax) provide beneficial algaecides and fungicides to water. Unfortunately, however, it is known that Boron derivatives promote the undesirable release of chlorine gas from the TCCA, as described above. For example, U.S. Patent No. 5,021,186 to Ota et al. Teaches that compositions comprising sodium tetraborate (9 g) and TCCA (21 g) generate 6.3 mg of chlorine gas, and compared to the 0.31 mg of gas generated for a similar amount of TCCA alone. Finally, it is known that in some situations the aluminum sulfates improve the stability of the chloroisocyanuric acids and consequently reduce the release of chlorine-containing gas from such compositions. The benefits of adding alum to TCCA are however limited, and are not believed to be enhanced by the addition of gas generating compounds such as boron derivatives to the alum / TCCA compositions. In fact, the opposite expectation has prevailed in the art, with the experts believing that the addition of boron derivatives to the alum / TCCA compositions could result in unsatisfactory levels of chlorine gas generation. Despite the known disadvantages of the use of chloroisocyanuric acid and borax in water treatment systems, a need continues for the trichloroisocyanuric acid compositions that take advantage of the beneficial algicidal and / or fungicidal properties of borax, which is even relatively safe and non-corrosive. The present invention is directed to that need.

BRIEF DESCRIPTION OF THE INVENTION Describing in summary the present invention, there are provided trichloroisocyanuric acid compositions having improved algicidal and / or fungicidal properties, which are even relatively safe and non-corrosive. The compositions contain 30% to 98% of TCCA, 0.2% to 15% glycoluril, 1% to 50% alum, and 1% to 50% borax. More preferably, the compositions contain between about 50% and about 95% of TCCA, between about 0.5% and about 7% of glycoluril, between about 2% and about 40% of alum and between about 2% and about 40% of borax. The compositions generate substantially less chlorine gas than would be expected from the teachings of the prior art, especially when wet. The compositions of the invention are therefore less toxic and less corrosive.

An object of the present invention is to provide the trichloroisocyanuric acid compositions having improved algicidal and / or fungicidal properties, which are relatively safe and non-corrosive. The additional objects and advantages of the present invention will be apparent from the following description.

DESCRIPTION OF THE PREFERRED MODALITY For purposes of promoting an understanding of the principles of the invention, reference will now be made to the preferred embodiments and the specific language will be used to describe them. However, it should be understood that no limitation of the scope of the invention is intended, such alterations and further modifications being contemplated in the described embodiments, and such additional applications of the principles of the invention as described herein, as would normally occur for someone of skill in the art, to which the invention belongs. As indicated above, the present invention relates generally to tablets of sanitization of trichloroisocyanuric acid. The compositions of the invention further contain aluminum sulfate and borax hydrate, to provide additional algicidal and / or fungicidal properties, do not even generate the expected levels of chlorine gas and are therefore relatively safe and non-corrosive. The compositions optionally contain glycoluril, and other components such as tabletting aids, mold release agents, corrosion inhibitors, scale inhibitors and / or dyes can be used. The relative proportions of the various components, as well as the potential substitutions for them, are described below. Representative examples of the preparation and use of the compositions are also presented. For chloroisocyanuric acid, trichloroisocyanuric acid ("TCCA" or "trichlor") is preferred, although dichloroisocyanuric acid may also be used. These two chemicals are raw material chemicals that are commercially available. In this patent document, the names trichloroisocyanuric acid, TCCA and trichloro are used interchangeably, since the most appropriate chemical name is trichloro-s-triazintrione.

The concentration of trichlor in the total formula is generally between about 30 and 98%. The trichlor is preferably present in an amount between about 50% and 95%; more preferably between about 65% and 90% of the total formula in bulk. In yet another aspect of the present invention, the TCCA is optionally partially or completely replaced with other slow-dissolving halogen sanitizers, such as l-bromo-3-chloro-5,5-dimethylhydantoin, 1,3-dichloro-5 , 5-dimethylhydantoin or other halogenated and / or alkylated hydantoins. The aluminum sulfate (alum) of the present invention is commonly provided having any of a variety of equivalent or different amounts of water of hydration. Any hydrate is acceptable for use in the invention; preferably, the alum having 2 to 20 equivalents of water per mole of aluminum sulfate is used. In the alternative embodiments of the invention, aluminum sulfate is a hydrated potassium alum or hydrated sodium alum. The concentration of aluminum sulfate can be varied from 1 to 50, or preferably from 2 to 40 percent of the total mass of the formula. In the most preferred embodiment, aluminum sulfate is present in an amount of between about 5% and about 30% of the total composition. The boron-containing component is preferably provided as a borax hydrate, a product that is commercially available with a variety of different equivalent amounts of water of hydration. Borax hydrates containing 3 to 18 equivalents of water, or preferably from 4 to 14 equivalents of water per mole of borax, are used more effectively. In addition, borax can be partially or totally replaced with other boron-containing compounds, such as boric acid or other borax oxygen oligomers. The concentration of sodium tetraborate (borax) can be varied from 1 to 50, or preferably from 2 to 40 percent of the total mass of the formula. In the most preferred embodiment, borax is present in the amount of between about 4% and about 20% of the total composition. The inclusion of glycoluril in the compositions of the present invention is optional. In the preferred embodiments, however, glycoluril is included in the formulation. The glycoluril can be substituted or unsubstituted, and is more preferably of the structure: where R-. and R.- each is selected from the group consisting of hydrogen, lower alkyl groups of 1 to 4 carbon atoms and phenyl; each X (where i = a, b, c, od) are selected from the group consisting of hydrogen, chlorine and bromine, and n is either 0 or 1. As used herein, the term "glycoluril" includes all the forms of glycoluril that fall within the previous formula. The term "non-substituted gl.coluril" refers only to the glycoluril according to the above formula, wherein each of R;, R? and X. is hydrogen. The glycoluril is preferably included in the amount of between about 0.2 and about 15 percent. Preferably from 0.5 to 7% giicoluril, more preferably from about IO to about 5%. The average particle size of the glycoluril is typically less than 500 microns. Dimethylhydantoin ("DKH") or other molecules containing imide and amide functional groups or halogenated analogs of these molecules can be used to either partially or totally replace the glycoluril.

The particle sizes of the other components of the mixture are typically less than 2.0 mm. The compositions of the present invention are preferably provided as a solid compressed product, and can be of virtually any size or shape. More preferably, the compressed product is shaped as a solid tablet, a bar or disc that is easily accommodated by the standard skimmer or cream skimmer baskets, chemical feeders or flotation release devices. For other uses, such as hot tubs, spas, lavatories and industrial applications, different sizes and / or shapes may be preferred. As previously indicated, additional components such as binders, tabletting aids, mold release agents, corrosion inhibitors, scale inhibitors or dyes can be incorporated into the tablets or discs. The selection of such components is within the ability of those skilled in the art. Reference will now be made to the specific examples using the processes described above. It must be understood that the examples are they provide to more fully describe the preferred embodiments, and that no limitation is intended to the scope of the invention.

EXAMPLES 1-16 General Procedure for Examples 1-16: Mixed products were prepared by weighing appropriate amounts of each constituent within a container. The container was then mixed perfectly. A one gram sample of the test formula contained in a 1.9 cm (0.75 inch diameter) metal cylinder was compressed with 181.4 kg (400 pounds) of force for 15 minutes. In some examples 9-16, a similar wafer was prepared to determine the impact of the water on the amount of gaseous oxidant released from the test formulas. The resulting small wafer was transferred to a 229.6 gram (8 ounce) container. A small container with 5 ml of a solution of potassium iodide (15%) was placed together with the wafer into the container. The container was sealed and placed in an oven that was heated (50-70 ° C). After approximately 16 hours, an aliquot of the KI solution was removed and titrated with 0.100 N sodium thiosulfate solution. of thiosulfate reagent used in the titration was recorded. The volume of thiosulfate used in this titration is proportional to the amount of gaseous oxidant (chlorine, chloramines, etc.) released from the sample. As can be seen from the following tables, compositions comprising TCCA, borax and alum generate significantly less chlorine gas than would be expected from data related to TCCA, alum and borax alone. In particular, for examples (1-8) where water is not added to the composition, it can be seen that while compositions comprising 25% alum generate chlorine gas which requires 0.53 ml of Na2S203 to be titrated, and since the Compositions that comprise 25% of borax generate chlorine gas that requires 5.44 ml of NaS03 to be titled, compositions comprising 12.5% borax and 12.5% alum generate chlorine gas that requires only 1.00 mi Na2S203 to be titled - much lower than the weighted average of gas generated by the two components. This result is unexpected, and is surprising in view of the teachings of the prior art. Similarly, since compositions comprising 12.5% alum generate chlorine gas that it requires 0.80 ml of Na2S203 to be titrated, and since the compositions comprising 12.5% of borax generate chlorine gas that requires 3.23 ml of Na2S203 to be titrated, the compositions comprising 12.5% borax and 12.5% alum generate chlorine gas that requires only 1.00 mi Na2S203 to be titled - much smaller than the additive amount of the two components. In the examples (9-16), where water is added to the composition, the result is equally surprising. In particular, it can be seen that while compositions comprising 25% of alum generate chlorine gas which requires 0.49 ml of Na2S203 to be titrated, and since the compositions comprising 25% of borax generate chlorine gas which requires 2.92 ml Na2S203 to be titrated , compositions comprising 12.5% borax and 12.5% alum, generate chlorine gas that requires only 0.97 ml of NaS203 to be titled - much lower than the weighted average of the gas generated by the two components. Similarly, while compositions comprising 12.5% alum generate chlorine gas that requires 0.57 ml of Na2S203 to be titrated, and since compositions comprising 12.5% borax generate chlorine gas that requires 3.00 ml of Na2S203 to be titled, compositions comprising 12.5% borax and 12.5% alum generate chlorine gas that it requires only 0.97 mi Na2S203 to be titled - much smaller than the additive amount of the two components. The following tables summarize the data.

Examples 1-8. Using the above general procedure, these formulas were mixed, wafers were prepared and the amount of gaseous oxidant released was quantified.

Examples 9-16. Using the above general procedure, these formulas were mixed, wafers were prepared, the wafer was contaminated with 0.1 ml of water, and the quantity of gaseous oxidant released was quantified.

EXAMPLES 17-24 General procedure for examples 17-24: Mixed products were prepared by weighing the appropriate amounts of each constituent inside a container, the container was then perfectly mixed in a Vee type mixer. A 100 g sample of the test formula was prepared for a 7.62 cm (three inch diameter) metal die. The formula was compressed for 0.2 minutes with 21 tons of pressure. The resulting disk was transferred to a 229.6 gram (8 ounce) container. A small container with 10 ml of a solution of potassium iodide (15%) was placed on top of the disc in the container. The container was sealed and placed in an oven (50-70 ° C). After approximately 16 hours, an aliquot of the KI solution was removed and titrated with a 0.100 N sodium thiosulfate solution. The volume of the thiosulfate reagent used in the titration was recorded. The volume of thiosulfate used in this titration is proportional to the amount of gaseous oxidant (chlorine, chloramines, etc.) released from the sample. Again, the results show an unexpected and surprising result when borax and alum are included in the composition of TCCA. In particular, while compositions comprising 25% of alum generate chlorine gas that requires 0.73 ml of Na2S203 to be titrated, and since the compositions comprising 25% borax generate chlorine gas that requires 2.05 ml Na2S203 to be titrated, compositions comprising 12.5% borax and 12.5% alum generate chlorine gas that requires only 0.68 ml of Na? S203 to be titled-less than the average weighted of the gas generated by the two components, and even less than the gas generated by the composition of TCCA / alum alone. Similarly, since compositions comprising 12.5% alum generate chlorine gas that requires 1.10 ml of Na2S203 to be titrated, and since compositions comprising 12.5% borax generate chlorine gas that requires 1.73 ml of Na2S203 to be titrated, compositions comprising 12.5% borax and 12.5% alum generate chlorine gas that requires only 0.68 ml Na2S203 to be titrated - much less than the additive amount of the two components and less than TCCA or TCCA / alum alone. A table summarizing the data is provided immediately.

Examples 17-24. Using general procedure 2, discs with the composition shown below were prepared, and the amount of chlorine gas released was quantified.

EXAMPLES 25-29 Several samples were subjected to the DOT oxidant test, in accordance with Section 173, Appendix F of the Code of Federal Regulations, Title 49 by the procedure described below. 30 grams of a mixture of the sawdust sample (softwood, 200 mesh), which contained mass proportions of 1 to 1 and 4 to 1, were prepared, placed in conical piles, and ignited by means of a heated wire at 1,000 ° C, until the first signs of combustion were perceived, or until it was clear that the battery could not be ignited. This was repeated 3 times for each mixing ratio.

Similar tests were performed using ammonium persulfate, potassium perchlorate, and potassium perbromate if necessary, each in a ratio of 1 to 1 with wood powder as reference materials. These tests were repeated twice more for a total of three tests per reference material. Based on the ignition time of the sample in relation to the reference materials, the sample was classified into packing or packaging groups, based on their relative danger. The relative oxidative hazard progresses in the order shown: Group I Packaging > Group II packaging > Group III packaging > Not Considered an Oxidizer The environmental conditions for the test were 20 ° C (68 ° F) and 35-45% relative humidity. The results of the tests are shown in the following Table.

It can be seen from Examples 25-29 that the inclusion of alum and borax in the compositions containing TCCA, makes the compositions safer with respect to their hazard in packing or packaging.

EXAMPLES 30-33: GENERAL PROCEDURE Mixed products were prepared by weighing the appropriate amounts of each constituent in a container. The container was then perfectly mixed. About 18 grams of the test formula were compressed under conditions to produce 2.54 cm (1 inch) diameter tablets, with a crush resistance comparable to commercial trichloro tablets.

Within a container, 8 tablets of the test formula (approximately 18 grams each) were stacked. Pool water was added to the container to completely submerge the tablets. The proportion of the sample to water was similar to that found in a typical gilder. The container was then sealed with a plug that allows gases from the upper space to be purged. The assembly was connected to a series of two gas scrubbers. Each treatment unit contained 50 ml of a 15% potassium iodide solution. A regulated flow of air was passed through the assembly to transfer the gases from the upper space to the scrubbers. The air flow was measured at the exit of the test system, to ensure that the flow rates were constant for each sample. After about 4 hours, the flow was stopped and the potassium iodide solution for the two scavengers was combined. The solution was titrated with a 0.0100 N sodium thiosulfate solution. The volume of thiosulfate used for each titration is proportional to the amount of gaseous oxidant (chlorine, chloramines, etc.) released from the sample. The concentration of chlorine corresponding to the volume of the thiosulfate used was calculated.

EXAMPLES 30-31 Using the above general procedure, the formulas were mixed, the tablets were prepared and the amount of gaseous oxidant released was quantified. The results are shown in the following Table.

Example V Voolluummeenn C Coonncc .. ,, M Maassaa ppHH Final pH of Na2S203 as Initial Total (mi) Chlorine (mq / 1) Sample (g) 100% TCCA 27.05 96 144.08 6.5 2.6 7% Borax 18% Alum 7.19 25 144.11 6.5 3.7 73% TCCA The amount of chlorine released by the tablets of the test formula was substantially lower than what would be expected based on the relative concentrations of the TCCA of the test substances.

EXAMPLES 32-33 5 Using the above general procedure, these formulas were mixed and the tablets were prepared. The pH of the pool water used was adjusted to 9.5. The amount of gaseous oxidant released was quantified, as shown in the following Table.

Example Volume Conc. Mass pH Final pH of Na2S203 as Initial Total (mi) Chlorine (mg / l) Sample (g) 100% TCCA 32.97 120 144.44 9.5 2.8 7% Borax 18% Alum 3.06 11 143.31 9.5 3.7 73% TCCA It can be seen from the foregoing that the amount of chlorine released by the tablets of the test formula was substantially lower than would be expected based on the relative concentrations of TCCA of the test substances. While the invention has been illustrated and described in detail in the drawings and the accompanying description, it should be considered as illustrative and not as restrictive, it being understood that only the preferred embodiment has been shown and described, and that all changes and modifications that come within the spirit of the invention, you want them to be protected.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims (31)

1. A sanitization and clarification product with a reduced propensity to generate chlorine gas, characterized in that it comprises: (a) between about 30% and about 98% trichloro-s-triazinetrione; (b) between about 1% and about 50% sodium tetraborate; and (c) between about 1% and about 50% aluminum sulfate.

2. The sanitization and clarification product according to claim 1, characterized in that the product comprises from about 50% to about 95% trichloro-s-triazinetrione.

3. The sanitization and clarification product according to claim 2, characterized in that the product comprises from about 65% to about 90% trichloro-s-triazinetrione.

4. The sanitization and clarification product according to claim 1, characterized in that the product comprises from about 2% to about 40% sodium tetraborate

5. The sanitization and clarification product according to claim 4, characterized in that the product comprises from about 4% to about 20% sodium tetraborate.

6. The sanitization and clarification product according to claim 1, characterized in that the product comprises from about 5% to about 40% aluminum sulfate.

7. The sanitization and clarification product according to claim 6, characterized in that the product comprises from about 2% to about 30% aluminum sulfate

8. The compositions according to claim 1, further characterized in that they comprise between about 0.5% and about 7% glycoluril.

9. The sanitization and clarification product according to claim 8, characterized in that the product comprises from about 0.5% to about 7% glycoluril.

10. The sanitization and clarification product according to claim 9, characterized in that the product comprises from about 1% to about 5% glycoluril.

11. The sanitization and clarification product according to claim 1, characterized in that the product also comprises boric acid.

12. The sanitization and clarification product according to claim 1, characterized in that the product also comprises a colorant.

13. A method for clarifying and sanitizing water, while minimizing the generation of undesirable chlorine gas, the method is characterized in that it comprises the addition to water of a sanitization and clarification product comprising: (a) about 30% to about 98% of trichloro-s-triazinetrione (b) about 1% to about 50% sodium tetraborate; and (c) about 1% to about 50% aluminum sulfate.

14. The method according to claim 13, characterized in that the sanitization and clarification product comprises from about 50% to about 95% trichloro-s-triazinetrione.

15. The method according to claim 14, characterized in that the sanitization and clarification product comprises from about 65% to about 90% of trichloro-s-triazinetrione.

16. The method according to claim 13, characterized in that the sanitization and clarification product comprises from about 2% to about 40% of sodium tetraborate.

17. The method according to claim 16, characterized in that the sanitization and clarification product comprises from about 4% to about 20% sodium tetraborate.

18. The method according to claim 13, characterized in that the sanitization and clarification product comprises from about 2% to about 40% aluminum sulphate.

19. The method according to claim 18, characterized in that the sanitization and clarification product comprises from about 5% to about 30% aluminum sulfate.

20. The method according to claim 13, characterized in that the product of sanitization and clarification further comprises from about 0.2% to about 15% glycoluril.

21. The method according to claim 20, characterized in that the sanitization and clarification product comprises from about 0.5% to about 7% glycoluril.

22. The method according to claim 21, characterized in that the sanitization and clarification product comprises from about 1% to about 5% glycoluril.

23. The method according to claim 13, characterized in that the sanitization and clarification product further comprises boric acid.

24. The method according to claim 13, characterized in that the product of sanitization and clarification also comprises a colorant.

25. A sanitization and clarification product with reduced propensity to generate chlorine gas, characterized in that it comprises: (a) a sanitizer containing halogen; (b) between about 1% and about 50% of a tetraborate compound; and (c) between about 1% and about 50% aluminum sulfate.

26. The sanitization and clarification product according to claim 25, characterized in that the halogen-containing sanitizer is a chloroisocyanuric acid or a halogen-containing dimethylhydantoin.

27. The sanitization and clarification product according to claim 26, characterized in that the halogen-containing sanitizer is a dichloroisocyanuric acid.

28. The sanitization and clarification product according to claim 26, characterized in that the halogen-containing sanitizer is l-bromo-3-chloro-5,5-dimethylhydantoin or 1,3-dichloro-5,5-dimethylhydantoin.

29. The sanitization and clarification product according to claim 25, characterized in that the halogen-containing sanitizer is a halogenated hydantoin.

30. The sanitization and clarification product according to claim 25, characterized in that the halogen-containing sanitizer is an alkylated hydantoin.

31. The sanitization and clarification product according to claim 25, characterized in that the tetraborate compound is a sodium or potassium tetraborate.