CA2178171A1 - Water preservative composition - Google Patents

Abstract

A water preservative composition for use in water-filled products, such as water-filled toys. More particularly, the present invention is a safe and effective water preservative composition providing long term protection against bacteria and fungi growth at divergent temperatures in water-filled toys made of plastic materials. The water preservative composition of the present invention comprises water, diazolidinyl urea, methyl p-hydrooxybenzoate, propyl p-hydrooxybenzoate, propylene glycol, triethylene glycol, benzyl alcohol and methylchloroisothiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-isothiazolone), magnesium chloride and magnesium nitrate.

Description

- 21781~1 WATER PRESERVATIVE COMPOSITION

DESCRIPTION

Technical Field The present invention generally relates to a water preservative composition. The composition is particularly suited for use in water-filled products. Particularly, the present invention relates to a safe and effective water preservative composition which may be used in water-filled toys, such as placemats used at a dinner table. More particularly, the present invention relates to a water preservative - 217817 l composition used in water-filled toys for the long-term prevention of bacteria and fungi growth at divergent temperatures.
Backqround of the Invention Many water preservative compositions for use in water-filled products, such as water-filled toys, are known in the art. For example, a composition comprising distilled water, chlorine and propylene glycol is widely used as a water preservative in a wide range of water-filled products, including products made of polyvinyl chloride (PVC). However, this composition is ineffective in preventing the formation of a wide variety of fungi and bacteria after an extended period of time. Since most water-filled products are novelty items and do not require long term preservation, this composition is still widely used where long term preservation is not a critical factor in the commercial success of the product.
Another known composition of distilled water and n-alkyl (Cl2-Cl8) benzyl dimethyl ammonium chloride (a quaternary ammonium compound manufactured by the Stepan Company under the trade name BTC 2125) is often recommended for bacteria growth problems in water-filled products. Although this composition appears to be effective in some cases, over time it does not 21781~1 -achieve consistent results. Many instances of bacteria contamination, algae or discoloration occur when the composition is used with products made of PVC.
Additional problems with inconsistent results in conjunction with PVC products also arise with the known composition containing distilled water and p-hydroxybenzoate esters in 2-phenoxyethanol (a preservative manufactured by NIPA Laboratories, Inc. under the trade name Phenonia).
Another known composition includes distilled water and an antimicrobial compound manufactured by M&T Chemicals under the trademark bioMeTTM 66.
bioMeTT~ 66 contains n-alkyl (C14C16C18) dimethyl benzyl ammonium chloride and bis (tri-n-butylin) oxide (manufactured by M&T Chemicals under the trademark bioMeT TBTO~M) and other inert ingredients known in the art. This particular composition yields a zero plate count at initial testing. However, when exposed to high temperatures, including temperatures of over 100~F for an extended duration, the composition becomes unstable, and fungi and bacteria can form as a result of this instability.
Other compositions known in the art were used by the inventors. Such compositions were found to yield high pH levels in the water or the chemicals were altered. This resulted in either a leaching of the ink in the water-filled products or continued bacteria or fungi growth.
One other potential solution, the continued use of commercial distilled water, proves neither cost effective nor guarantees contaminant-free water.
Summary of the Invention It is an object of the present invention to provide a safe and effective water preservative composition with improved antimicrobial components for use in conjunction with water-filled products, such as water-filled toys. The present invention may be used with a wide variety of water-filled toys, including placemats to be used at a dinner table. The present composition comprises chemical components which are cleared with the Environmental Protection Agency and are safe for use by children at the dinner table.
It is a further object of the present invention to provide a water preservative composition which is effective against a wide spectrum of bacteria and fungi, including Gram-positive and Gram-negative organisms, yeasts and mold. The present invention may be used in water-filled products made of plastic materials, including PVC.

-It is also an object of the present invention to provide a water preservative composition which consistently provides long-term protection against bacteria and fungi growth at divergent temperatures. The water preservative composition of the present invention is effective indefinitely or until natural osmosis occurs and the water is no longer present.
The present invention also provides a method of deionization filtration and ultraviolet (W) light exposure so that water received from a municipal source may be used to produce water free of contaminants. The deionization filtration system for tap water, including either deionization or a combination of reverse osmosis with deionization, followed by exposure to W
light, proves to be effective and less costly to maintain than using commercial distilled water.

Other advantages and aspects of the present invention will become apparent upon reading the following description of the drawing and detailed description of the invention.

Brief Description of the Drawing Figure 1 illustrates a view of the preparation process of the present invention.
Detailed Description This invention is susceptible of embodiment in many different forms. Shown in the drawing and the preferred embodiments are certain methods of manufacture. The present disclosure is to be considered an exemplification of the principles of the invention, and is not intended to limit the broad aspect of the invention to the embodiments illustrated.
All listed percentages of components are weight percentages of the water preservative composition, unless otherwise indicated.
According to one aspect of the present invention, there is provided a water preservative composition comprising diazolidinyl urea, methyl p-hydrooxybenzoate, propyl p-hydro-oxybenzoate, propylene glycol, benzyl alcohol and methylchloro-isothiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-iscthiazolone).
According to another aspect of the present invention, there is provided a water preservative composition containing the following components: water, diazolidinyl urea, methyl p-hydrooxybenzoate, propyl p-hydrooxybenzoate, propylene glycol, triethylene glycol, benzyl alcohol, methylchloroiso-thiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-isothiazolone), magnesium chloride and magnesium nitrate.

According to a further aspect of the present invention, there is provided a method of preparing a water preservative composition comprising the steps of: removing ionized solids in water by deionization filtration; adding antimicrobial chemical components to the deionized water;
thoroughly blending the composition to evenly distribute the components in the composition.
The diazolidinyl urea component used in the present invention has the molecular formula C8H14N407 and is manufactured by Sutton Laboratories, Inc. and sold under the trade-mark 6a Germall~ II. Sutton Laboratories, Inc. also manufactures an antimicrobial preservative system under the trademark Germaben~ II, comprising certain additional components including, diazolidinyl urea, methyl p-hydrooxybenzoate, propyl p-hydrooxybenzoate and propylene glycol.
Germaben~ II comprises about 30~ by weight diazolidinyl urea, about 11~ by weight methyl p-hydrooxybenzoate, about 3~ by weight propyl p-hydrooxybenzoate, and about 56~ by weightpropylene glycol.
The methyl p-hydrooxybenzoate component of the present invention is also known as methylparaben, and has molecular formula C8H8O3.
The propyl p-hydrooxybenzoate component is also known as propylparaben, and has the molecular formula C1oH12O3~ Paraben~ is a trademark for the methyl, propyl, butyl and ethyl esters of p-hydrobenzoic acid used as antimicrobial agents for foods and pharmaceuticals. Propylene glycol is added as an antimicrobial solvent and has the molecular formula C8H8O3.
The additional components of the present invention include, benzyl alcohol, having the m o l e c u l a r f o r m u l a C 7 H 8 ~ ' methylchloroisothiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-isothiazolone), triethylene glycol, having the 217~171 molecular formula C6Hl4O4, propylene glycol, having the molecular formula C8H8O3, magnesium chloride, having the molecular formula MgCl2, and magnesium nitrate, having the molecular formula Mg(NO3) 21 and water. These components are manufactured by Schulke & Mayr under the trade name Euxyl K 100.
Euxyl K 100 comprises about 20~ by weight benzyl alcohol and about 0.7-0.8~ by weight methylchloroisothiazolinone consisting of about 0.5-0.6~ by weight 5-chloro-2-methyl-3-(2H)-isothiazolone and 0.2~ by weight 2-methyl-3-(2H)-isothiazolone.
The quantitative information regarding the additional components of Euxyl K 100 are proprietary. However, the benzyl alcohol, an antimicrobial solvent, is an active component and methylchloroisothiazolinone (chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-isothiazolone) is also an active component, functioning as an antibacterial and antiparasitic component.
Tests were conducted to ascertain the acceptable ranges of water preservative composition which could be used to achieve consistent negative microbial growth results.
These acceptable ranges were arrived at by preparing aliquots from individual samples containing unfiltered tap water and adding various levels of the water preservative composition to the samples. The samples were incubated at 28-30~C and tested for microbial growth by streaking on agar petri plates at intervals of 48 hrs. and 7 days after the addition of the water preservative composition.
Certain samples were also inoculated with microorganisms following the initial 7 day test period and streaked again after 48 hrs. and after 7 days. All streaked petri plates are incubated for 7 days at 28-30~ C and 85~ relative humidity and examined for microbial growth.
Example I illustrates the test results at the indicated intervals. The numerical levels of microbial growth are rated according to the following legend:
4 = heavy microbial growth 3 = moderate microbial growth 2 = slight microbial growth 1 = trace microbial growth 0 = no microbial growth 217817~

EXAMPLE I

% BY WEIGHT ADDITION OF THE INOCULATION
COMPOSITION WATER WITH MICRO-PRESERVATIVE ORGANISMS
COMPOSITION
48 7 days 48 hrs. 7 days ~ hrs.
0.0~ - 4 4 4 4 UNFILTERED
TAP WATER
0.63~ 0 0.885~ 0 0 1.14% ~ ~ ~ ~
1.395~ 0 0 0 0 1.65~ ~ ~ ~ ~

The effective level of water preservative composition is the lowest concentration which produced no microbial growth within 7 days of the addition of the water preservative composition and inoculation. A sample which has no microbial growth after 7 days is adequate for short term storage, i.e., less than 3 months. A sample which has no microbial growth within 7 days of both the addition of the water preservative composition and inoculations, is adequately protected for long term storage, i.e., greater than 6 months.
Table I illustrates the components of the by weight composition tested:

-TABLE I
~ BY WEIGHT GERMABEN~II GERMALL~II EUXYL K

0.63~ 0.50~ 0.10~ .03 0.855~ 0.625% 0.20~ 0.06 1.14~ 0.75~ 0.30~ 0.09 1.395~ 0.875~ 0.40~ 0.12 1.65~ 1.00~ 0.5~ 0.15~

The above tests were also conducted on varying degrees of the least and greatest acceptable limit of water preservative composition added to the water under ideal conditions. Specifically, under ideal conditions, all filters are carefully monitored and adequate measures for cleanliness are maintained. The tests indicated that the lower percentages of the water preservative composition which may produce trace microbial growth when added to unfiltered tap water are effective when distilled water or water which is deionized and exposed to W light is used in place of unfiltered tap water.
The preferred water preservative composition of the present invention contains about: 0.50-1.00~ by weight Germaben~ II, about 0.10-0.50~ by weight Germall~ II, about 0.03-0.15~ by weight Euxyl K 100, and about 98.35-99.37~ by weight water. TAB~E II illustrates the acceptable ranges of commercially available components:

217~171 TABLE II
WATER MIN MAX
PRESERVATIVE
COMPOSITION
5GER ~3ENTM II 0.50~ 1.00 GERMALLTM II 0.10~ 0.50 EUXYL K 100 0.03~ 0.15 WATER 98.35~ 99.37~

The ranges of commercially available components correspond to about: . 25%-0.80~ by weight diazolidinyl urea, about 0. 055-0.110~ by weight methyl p-hydrooxybenzoate, about 0. 015-0.030~ by weight propyl p-hydrooxybenzoate, about 0.28-0.56~ by weight propylene glycol, about 98.35~-99.37~ by weight water. The minimum and maximum ranges of Euxyl K 100 are also provided.
Euxyl K 100 is added 0. 03-0.15~ by weight, containing 0. 006-0.030~ by weight benzyl alcohol, 0.00021-0.0012~ by weight methylchloroisothiazolinone ( 5- chloro- 2 -methyl- 3-(2H)- isothiazolone and 2 -methyl- 3-(2H)-isothiazolone), and 0. 02379-0.1188~ by weight propylene glycol, triethylene glycol, magnesium chloride and magnesium nitrate.

-TABLE III illustrates the acceptable ranges:
TABLE III

CHEMICAL MIN MAX
COMPONENT
diazolidinyl urea 0.25~ 0.80 methyl p- 0.055~ 0.110 hydrooxybenzoate propyl p- 0.015~ 0.030 hydrooxybenzoate propylene glycol 0.28~ 0.56 Euxyl K 100 0.03~ 0.15 water 98.35~ 99.37~

EUXYL K 100MIN (0.03~) MAX (0.15~) BENZYL ALCOHOL0.006~ 0.030 METHYLCHLORO-0.00021% 0.0012 ISOTHIAZOLINONE

PROPYLENE 0.02379~ 0.1188 GLYCOL, TRIETHYLENE
GLYCOL, MAGNESIUM
CHLORIDE, MAGNESIUM
NITRATE AND
WATER

The above test concluded the ranges of the water preservative composition which could be used to achieve negative results in (zero microbial growth) all test samples. However, percentages of a preferred formula were derived from conducting the following test:

217~171 EXAMPLE II

4 kg. Germaben~ II was combined with 3.2 kg.
Germall~ II and 0. 5 kg. Euxyl K 100 and 800 liters water. The composition was blended thoroughly to assure even distribution of the chemicals. The formula was dispensed into a placemat made of PVC material.
After running multiple tests at various temperatures, the test results indicate that the preferred composition achieves consistent zero microbial growth in all test samples.
The preferred formula comprises about:
0.50~ by weight Germaben~ II;
0.40~ by weight Germall~ II;
0.0625~ by weight Euxyl K lOo; and, 99.0375~ by weight water.
The components of the preferred formula correspond to about:
0.550~ by weight diazolidinyl urea;
0.055~ by weight methyl p-hydrooxybenzoate;
0.015~ by weight propyl p-hydrooxybenzoate;
0.280~ by weight propylene glycol;
0.0625% by weight Euxyl K 100; and, 99.0375~ by weight water.
The method of making a water preservative composition in accordance with the principles 217~171 of the present invention will now be described below. As illustrated in FIGURE I, in one aspect of the present invention, water is received from a municipal source and deionized and exposed to W light. A known and preferred deionization filtration process effective in removing ionized solids by ion exchange, is manufactured and sold by Culligan, Inc. and sold under the trade name Portable Exchange.
This preferred process, involves removing both the negatively charged ions and the positively charged cations by a charged ion exchange resln .
W light exposure assists in eliminating a wide variety of bacteria and fungi present in water received from a municipal source. The preferred W light apparatus is also manufactured and sold by Culligan, Inc.
The tap water received from most municipalities has an acceptable bacteria range of 300-350 ppm. The preferred process of deionization filtration along with W light exposure removes up to 99.0~ of the minerals and contaminants present in the water.
As further illustrated in FIGURE I, after the water component of the present invention is deionized and exposed to W light, the chemical components of the water preservative composition are then added to the treated water in a batch process. The processed water is contained in a 800 liter tank and thoroughly blended. The chemical components including diazolidinyl urea, methyl p-hydrooxybenzoate, propyl p-hydrooxybenzoate, propylene glycol, benzyl alcohol and methylchloroisothiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-isothiazolone) are added to the processed water.
After the addition of the chemical components, the composition is continuously blended to ensure even distribution of the chemicals. The composition is then dispensed into the water-filled product.
While the specific embodiments have been illustrated and described, numerous modifications come to mind without markedly departing from the spirit of the invention.
The scope of protection is only intended to be limited by the scope of the accompanying claims.

Claims (17)

1. A water preservative composition comprising diazolidinyl urea, methyl p-hydrooxybenzoate, propyl p-hydrooxybenzoate, propylene glycol, benzyl alcohol and methylchloroisothiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-isothiazolone).

2. The composition of Claim 1, wherein the composition further comprises water.

3. The composition of Claim 2, wherein the composition further comprises triethylene glycol.

4. The composition of Claim 2, wherein the composition further comprises magnesium chloride.

5. The composition of Claim 2, wherein the composition further comprises magnesium nitrate.

6. The composition of Claim 2, wherein the composition comprises about 0.25-0.80% by weight diazolidinyl urea.

7. The composition of Claim 2, wherein the composition comprises about 0.055-0.110% by weight methyl p-hydrooxybenzoate.

8. The composition of Claim 2, wherein the composition comprises about 0.015-0.030% by weight propyl p-hydrooxybenzoate.

9. The composition of Claim 2, wherein the composition comprises about 0.006-0.030% by weight benzyl alcohol.

10. The composition of Claim 2, wherein the composition comprises about 0.00021-0.0012%
by weight methylchloroisothiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-isothiazolone).

11. The composition of Claim 2, wherein the composition comprises at least 0.28% by weight propylene glycol.

12. The composition of Claim 2, wherein the composition comprises about 0.25-0.80% by weight diazolidinyl urea, about 0.055-0.110% by weight methyl p-hydrooxybenzoate, about 0.015-0.030% by weight propyl p-hydrooxybenzoate, about 0.006-0.030% by weight benzyl alcohol, about 0.00021-0.0012% by weight methylchloroisothiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-isothiazolone), at least 0.28% by weight propylene glycol and water to form a 100% by weight composition.

13. A water preservative composition comprising diazolidinyl urea, methyl p-hydrooxybenzoate, propyl p-hydrooxybenzoate, propylene glycol, benzyl alcohol, triethylene glycol, methylchloroisothiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-isothiazolone), magnesium chloride and magnesium nitrate and water.

14. A method of preparing a water preservative composition comprising the steps of:
removing ionized solids in water by deionization filtration;
adding antimicrobial chemical components to the deionized water;
thoroughly blending the composition to evenly distribute the components in the composition.

15. The method of preparing a water preservative composition of claim 14, further comprising the step of:
removing contaminants by exposing the water to ultraviolet light.

16. The method of preparing a water preservative composition of claim 14, wherein the components comprise water, diazolidinyl urea, methyl p-hydrooxybenzoate, propyl p-hydro-oxybenzoate, propylene glycol and benzyl alcohol, triethylene glycol, methylchloroisothiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-iscthiazolone), magnesium chloride and magnesium nitrate.

17. The method of preparing a water preservative composition cf claim 14, wherein the components comprise about 0.25-0.80% by weight diazolidinyl urear about 0.055-0.110% by weight methyl p-hydrooxybenzoate, about 0.015-0.030% by weight propyl p-hydrooxybenzoate, about 0.006-0.030% by weight benzyl alcohol, about 0.00021-0.0012% by weight methylchloroiso-thiazolinone (5-chloro-2-methyl-3-(2H)-isothiazolone and 2-methyl-3-(2H)-isothiazolone), at least 0.28% by weight propylene glycol and water to form a 100% by weight composition.