Note: Descriptions are shown in the official language in which they were submitted.
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LI~ID 1.2-~NZOISOT~IAZO~I~E-~-ONE P~EP~RATI~
Field of the Invention
The invention relates to a liquid preparation
of 1,2-benzoisothiazoline-3-one (BIT) with an amine.
Back~round of the InY~n~lQ~
The 1,2-benzoisothiazoline-3-one (BIT) has been
known as anti-microbially active substance and is used as
preservative in technical applications or, in general, as
an additive which is suitable to counteract material
destruction ("Mikromatz", in german) caused by microbes.
To make this compound available in a convenient
preparation that can be metered easily, an aqueous
dispersion may be prepared with the crude BIT obtained
during synthesis. Such dispersions, however, are not
stable when stored and will settle in the course of time.
GB Patent 11 91 253 has disclosed aqueous solutions of
crude BIT with two or more amine compounds of the series
comprising the diethanol amine, triethanol amine,
diisopropanol amine, triisopropanol amine or morpholine
these aqueous solutions contain BIT in the form of a
mixture of the amine salts. Furthermore, GB Patent 13 30
531 has disclosed that BIT amine salts can be imparted
with better stability in a cold environment when they are '
present in the form of solutions in aliphatic,
cycloaliphatic or heterocyclic amines having 2 to 60 C
atoms and do not have hydroxyl and ether groups. The
effectiveness of these preparations against material
destruction, however,frequently is not adequate.
Summ~y of the Invent;,o~
The present invention provides a
liquid preparation of ~,2-benzoisothiazoline-3-one (BIT)
and amines, and optionally with a content of additional
solvents and common additives, characterized in that it
contains, as an amine, one or more amines haviny the
~eneral formula
. ~ , . . . - . :
.: . . ; : ~ .
, .. .
~' ~
-2- ~ ~ , 3 ~ ? f.
(CH2 ) n ~ NH2
R-N <
(CH2)m-NH2
wherein R represents a straight-chained or branched alkyl
or alkylene radical having 6 to 22 C atoms and n + m has
a value of 4 to 12.
The invention provides new l:iquid preparations
of BIT and amines which are stable on storage and exhibit
a surprising synergistic effect against microbial
destruction in technical applications in technical
applications is suggested, in particular in technical
products which contain water or can be diluted with
water. The~ can be made into stable products with only
water as solvent, and therefore are more suitable from
the viewpoints of ecology, as well as human toxicology.
Detailed Description of the Invention
The preparations of the invention herein may
consist on one hand only of BIT and one or more amines
having Formula I and not contain additional solvents. In
~; this case, the BIT content is restricted to a maximum of
;~ 10~ by weight to improve keeping and handling properties.
On the other hand, preparations with a higher
BIT concentration and amines in accordance with Formula I
may be provided with one or more additional solvents.
~; Solvents which can be used, other than water
are solvents which can be mixed with water such as low-
molecular univalent, divalent and trivalent alcohols,
glycols, di- and polyglycols, ether or glycols, di- and
polyglycols such as ethanol, isopropanol, propanediol-
l,3,glycerin, butanetriol-1,2,3,butanetriol-
1,2,4,ethylene glycol, diethylene glycol, triethylene
glycol, polyethylene glycol, dipropylene glycol, ethylene
glyco]. monomethylether, ethylene glycol monoethylether,
ethylene glycol monopropylether, ethylene glycol
monobutylether, diethylene glycol monomethylether,
,
"~ : ~
--3--
diethyl glycol momoethylether, diethylene ~lycol
monopropylether, diethylene glycol monobutylether,
diethylene glycol dimethylether and diethylene glycol
diethylether, whereby the use of dipropylene glycol and
butyl digycol are preferred. Dihydroxyethylglycin sodium
salt is also useful.
Li~uid preparations containing BIT and organic
amines in accordance with Formula I and optionally other
solvents should have a molecular ratio of BIT relative to
the amines of at the most 3:1. With this concentration
ratio, the entire BIT is converted into its amine salt.
In the case o-f an amine having Formula I, where R =
lauryl and m + n = 3, this means a ratio of 10 parts by
weight of BIT to 6.6 parts by weight of amine. This
weight ratio is attained in accordance with
representative preparations 1 through 5 and 9 of
following Table 1.
Useful organic amines having Formula I include
those wherein R is C6- through C22- and, preferably C1o-
through C1~-, straight-chained or branched alkyl or
alkenyl amines such as, for example, derivatives of fatty
amines R-NH2, where R represents a coconut fat alkyl-(Cg
to C1g), (predominantly C12- to C1~- alkyl-), an oleyl
(predominantly Clg-alkeny~ a stearyl-(C16- to C1g-
alkyl-) or a tallow fatty alkyl radical (C16- to C1g-
alkyl- or akenyl-). These products are commercially
available and, as far as the length of the chain is
concerned, can be used either having a broad or narrow C
atom distribution.
Particularly preferred are preparations where
the amine compounds having Formula I have as substituent
R a lauryl radial and n + m have a value of 3. Such
amines are used preferably in an amount of 3 to 60%,
together with approximately 5 to 35% by weight of BIT, in
addition to the solvent, wherein the solvent consists
essentially of ylycols and advantageously even of water,
, . .
3 e~ ~t`
--4-
including dilute (0.5% by weight) sodium hydroxide
solutions. For example, such a composition may consist
of 5 to 30% by weight of BIT, 3 to 20% by weight of an
amine having Formula I, 25 to 4~% by weight of a glycol-
containing solvent and 67 to 10% by weight of water.
In another embodiment, a preparation of the
invention, in particular when producing low-emission
preparations, may contain more or less organic solvents,
whereby, in order to obtain preparations which are stable
in a cold enviror~ent and when stored, the amine compound
should be used in at least twice the amount necessary for
BIT salt formation. For example, such a composition
would then contain 5 to 20~ by weight of BIT and 6.5 to
26% by weight of the organic amine compound having
Formula I and 88.5 to 54% by weight of water.
Other conventional additives may be nonionic,
cationic and/or anionic surfactants used as emulsifying
or dispersing agents or as solubilizers, whereby the
amount of said additives is up to 25%, and preferably, 5
to 25% and, in particular 10 to 20%.
Additional additives may be known complexing
agents and/or water-softening agents which are suitable
for complexing calcium, magnesium or iron ions. The
contents of these additives usually is below
approximately 15% by weight and, preferably, not above
10% by weight, with respect to the preparation.
Furthermore, conventional additives may be color-
imparting additives, aromatic substances, turbi~ity-
providing substances and, of course, other disinfecting
components.
The liquid preparation of the invention herein
is suitable for use in industrial products which contain
water or can be mixed with water and are used against
destruction by microbes, in particular in liquid systems
such as, for example, in the case of dispersions of
synthetic materials using polystyrene, polyacrylate or
, `' ~, '. ' ~''
--5--
polyvinyl acetate and further in dyes, adhesives, paper-
coating materials, textile-plasticizing and sizing
agents, in crucle detergents, cleaning and polishing
agents, spinning baths, cold lubricants, leather-
processing agents and in silicone and bitumen emulsions.
The inventive preparation is preferably used ina concentration of 0.05 to 0.3% by weight, with respect
to the substrate to be preserved.
Apart from the principal inventive liquid
: 10 preparation which, in the simplest case, consists of 10%
by weight of BIT and 90% by weight of the amine compound
and represents a highly viscous clear solution which may
be combined with additional additives, the ~ollowing
Preparations of Table 1 provide more detailed
information, whereby the concentration data relate to the
:~ content of active ingredients. In order to prepare the
liquid preparations of the invention, it is useful if the
amine compound is first mixed with the solvents and any
. optionally required auxiliary substances, followed by the
addition of BIT and stirring at temperatures of 40 to
50 C until a clear solution is attained.
~.~
Pre~aration 1 Weiah~_%
1,2 benzoisothiazoline-3-one 35
; lauryldiproplylenetriamine 23
dipropylene alycol 22
butyl digycol 20
Pre~ara~ion 2
1,2 benzoisothiazoline-3-one 10
lauryldiproplylenetriamine 6.6
dipropylene glycol 83.4
1,2 benzoisothiazoline-3-one 30
lauryldiproplylenetriamine 20
dipropylene glycol 38
water 12
, ~
Pre~axation 4
1,2 benzoisothiazoline-3-one 5
lauryldiproplylenetriamine 3.3
butyl digycol 50
1,2-propylene glycol 25
water 16.7
Pre~a~ation 5
1,2 benzoisothiazoline-3-one 10
lauryldiproplylenetriamine 6.6
dipropylene glycol 50
water 33.4
Pre~aration 6
1,2 benzoisothiazoline-3-one 10
lauryldiproplylenetriamine 13.2
water 76.8
Pre~ara~ion 7
1,2 benzoisothiazoline-3-one 18
lauryldiproplylenetriamine 35
water 47
Pre~aration 8
1,2 benzoisothiazoline-3-one 20
lauryldiproplylenetriamine 26
water 54
Pre~aratign 9
1,2 benzoisothiazoline-3-one 10
lauryldiproplylenetriamine 6.6
water 63.4
ethoxylated fatty alcohol with 11 EO 20
PreDaration 10
Benzisothiazolone 10
Laurylpropylidentriamine 18
Dihydroxyethylglycin sodium salt 20
5 Sodium hydroxide 0.5
Water to 100
The synergistic effectiveness increase achieved
with the inventive preparations is obvious from the
results of a dilution test series which was performed
with a preparation of the invention and compared with the
efEectiveness individual substances of that same
preparation.
The test was carried out in accordance with the
guidelines of the Deutsche Gesellschaft fur Hygiene und
.
V'~' ',?j
--7--
Mikrobiologie (German Association for Hygiene and
Microbiology). The steps of dilution ranged from 5000,
2500, 1250 to 9.8 ~g/mL. The tested germs were:
Staphylococcus aureus ~Staph. aureus~
Pseu~omonas aeruginosa ~Ps. aeruginosa)
Candida albicans (C. albicans)
Penicillium funiculosum (P. funiculosum)
Aspegillus niger (A. Niger)
The minimum inhibiting concentrations (MIC
values) of Example A representing an inventive
preparation, Examples B and C containing only the
component benzoisothiazoline-3-one, and Example D
containing only the component lauryldipropylenetriamine
were determined.
Inventive ~xample A was contained 10% of
benzoisothiazoline-3-one, 10% of
lauryldipropylenetriamine, 30% of dipropylene glycol and
50% of water.
Reference Example B in accordance with DE
Patent 2~ 40 273 contained 10% of benzoisothiazoline-3-
one, 5.9% of sodium hydroxide solution (45%), 30% of
dipropylene glycol and 54.1% of water.
Reference Example C in accordance with GB
Patent 11 92 253 contained 10% of benzoisothiazoline-3-
one, 6.7% o~ ethylene diamine, 30% of dipropylene glycol
and 53.3% of water.
Reference Example D contained 10% of
lauryldipropylenetriamine, 30% of dipropylene glycol and
60% of water.
In order to demonstrate the synergism, the
synergism index, (SI) was calculated in accordance with
F. C. Kull, P. C. Eisman, H. D. Slverstrowicz and R. L.
Mayer, ~pplied Microbiology 9 (1961)538, according to the
following formula:
' ' . '
. ~: . ; . ~
'
- -
--8 ~ " ;~
QA QB
~ _ = S :~
Qa Qb
wherein Qa and Qb~ xespectively, represent the amount of
components A and B alone, respectively; and QA and QB~
respectively, represent the amount of the respective
component in a mixture of A and B which is required to
arrive at a defined end point.
If SI < 1, a synergism exists: in the case of a
SI = 1 a strictly additive effect is achieved; and a SI >
1 represents an antagonism.
At the end point of this dilution test series
that concentration must be set which just barely still
inhibits the growth of the micro-organisms, i.e., minimum
inhibiting concentration (MIC).
Therefore, in order to calculate the SI values,
the MIC values of the tested exarnples can be related to
each other.
MIC Example ~ MIC Example
SI
MIC Examples B or C MIC Example D
The SI values listed in the table below
illustrate the presence of a synergism. It is
particularly distinct in the case of the germs Ps.
aeruginosa and A. niger which are particularly relevant
in practical applications. The result compared with
known BIT formulations oEfers a more balanced spectrum of
efficacy with lower concentrations of active components.
30 Germ ~X~ MIC Values ~g/ml]
A B C D SI
Staph. aureus 78 312 312 625 0.38
; Ps. aeruginosa 312 2500 2500 2500 0.25
C. albicans 156 312 312 5000 0.53
P. funiculosum 78 156 156 5000 0.52
A. niger 312 1250 1250 5000 0.31
: . . : .
,
. ' . .
- . : . . . .
_ 9 _ ~J ~
The invention has been described in detail with
particular reference to certain preferred embodiments
thereof, but it will be understood that variations and
modifications can be effected within the spirit and scope
of the invention.
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