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Patent 2178171 Summary

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(12) Patent Application: (11) CA 2178171
(54) English Title: WATER PRESERVATIVE COMPOSITION
(54) French Title: COMPOSITION PROTEGEANT CONTRE L'EAU
Status: Dead
Bibliographic Data
(51) International Patent Classification (IPC):
  • A01N 47/28 (2006.01)
  • A01N 43/78 (2006.01)
  • A01N 59/06 (2006.01)
(72) Inventors :
  • PANTALEO, TERESE A. (United States of America)
(73) Owners :
  • PANTALEO, TERESE A. (United States of America)
(71) Applicants :
  • PANTALEO, TERESE A. (United States of America)
(74) Agent: SMART & BIGGAR
(74) Associate agent:
(45) Issued:
(22) Filed Date: 1996-06-04
(41) Open to Public Inspection: 1997-10-30
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
08/639,801 United States of America 1996-04-29

Abstracts

English 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.


Claims

Note: Claims are shown in the official language in which they were submitted.


C L A I M S
I claim:
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.


17




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,


18



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.


19




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.





Description

Note: Descriptions are shown in the official language in which they were submitted.


- 21781~1

579 P 031 PATENT




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

217S171

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.

2178171
-



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.


2178171

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.



69179-84

2178171

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




69179-84

- 2178171
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


2178171

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:





2178171
-



TABLE I
~ BY WEIGHT GERMABEN~II GERMALL~II EUXYL K
COMPOSITION 100
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.


2178171
-



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

14

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

2178171

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.


Representative Drawing
A single figure which represents the drawing illustrating the invention.
Administrative Status

For a clearer understanding of the status of the application/patent presented on this page, the site Disclaimer , as well as the definitions for Patent , Administrative Status , Maintenance Fee  and Payment History  should be consulted.

Administrative Status

Title Date
Forecasted Issue Date Unavailable
(22) Filed 1996-06-04
(41) Open to Public Inspection 1997-10-30
Dead Application 1999-06-04

Abandonment History

Abandonment Date Reason Reinstatement Date
1998-06-04 FAILURE TO PAY APPLICATION MAINTENANCE FEE

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1996-06-04
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
PANTALEO, TERESE A.
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Cover Page 1996-09-12 1 15
Claims 1996-09-12 4 101
Abstract 1996-09-12 1 19
Cover Page 1997-11-21 1 46
Drawings 1996-09-12 1 15
Description 1996-09-12 17 476
Office Letter 1996-06-28 1 12
Office Letter 1996-07-11 1 9
Prosecution Correspondence 1996-06-20 1 22
PCT Correspondence 1996-07-09 1 38
Representative Drawing 2000-12-07 1 5
Representative Drawing 1997-11-21 1 5
Cover Page 2000-12-07 1 46