CA1050880A

CA1050880A - Compositions having sanitizing and algaecidal properties

Info

Publication number: CA1050880A
Application number: CA240,918A
Authority: CA
Inventors: Roger C. Hollenbach; Harry M. Castrantas
Original assignee: FMC Corp
Current assignee: FMC Corp
Priority date: 1974-12-23
Filing date: 1975-12-02
Publication date: 1979-03-20
Also published as: ES443783A1; FR2295761B1; AU8723175A; BE837038A; FR2295761A1; AU498154B2; DE2558181A1; GB1494869A; ZA757978B; NZ179533A; JPS5186122A; IT1051851B

Abstract

ABSTRACT:
A composition is described containing sodium di-chloroisocyanurate dihydrate as a source of sanitizing chlorine, and a quaternary ammonium salt algaecide.
The inventive composition provides an improvement in stability and in safety from fire and explosion, com-pared to other chlorine releasing agent-organic al-gaecide compositions. Such compositions are useful in combining sanitizing action with persistent algaecidal activity when added to aqueous solutions, such as in swimming pools.

Description

~ FMC 1628 lOS0880 ~`
This invention relates to a composition which ~ ~
provides an improvement in stability and in safety ~ ;
from fire and explosion, over other compositions ;~`
of chlorine releasing agents and organic algaecides `~
used for sanitizing and for controlling algae growth in aqueous solutions, such as :in swimming pools.
Compositions containing chlorine releasing agents, such as chlorine dry bleach salts, which give off available chlorine when placed in water, , ~ ~
! ~ and organic algaecides, such as quaternary ammon-~ ium salts, are known and have been in commercial `
:::
use. Such compositions have the advantage of 1- `~
: .
combining sanitizing action with persistent algae-cidal activity when added to aqueous solutions, such as in swimming pools. The quaternary am~
monium chlorides are less effective algaecides and poor bactericides compared to chlorine re-aslng agents. However, their activity is ;~
20 not depleted as quickly as that of chlorine ;
releasing agents, and thus their main advantage i9 in providing continuing resistance to algae `~
growth as chlorine levels become depleted. -I
I~ ~ U. S. Patent 3,201,311 describes compositions ; - ; -f'~ containing mixtures of quaternary ammonium salts and chlorine releasing agents in which s plurality~of quaternary ammonium salts is em-ployed to obtain 1mproved results. ~;

~ Problems have arisen involving stability and -i~ 30 hazard from compositions o chlorine releàsing :'''; ~ ' .. . . . ... . . .. .

1050~
agents and quaternary ammonium salts; such compo-sitions decompose faster than either ingredient alone. ~ ;
There has been an expressed concern and desire by those in the industry for chlorine releasing agent-organic algaecide compositions which are stable and which do not present serious hazards from fire or explosion. ;
In accordance with the present invention there is provided a chlorine releasing agent-organic algaecide composition having greater stability and safety than previous compositions and which is useful as a sani-tizer and algaecide. The composition comprises the following (a) and (b) components in percent by weight based on the combined weight of (a) and (b):
(a) About 1 to about 99% o sodium dichloroiso- ~ ~
~, cyanurate dihydrate; and ~ -(b) About 99 to about 1% of a quaternary ammonium salt of the following general formulae, (i) and R4 - N - R2 ~ X-n(H20) \ R3 ~ m wherein X is selected from the group consisting of Cl , S04 and P0,~~, m is an integer from 1 to 3, n is zero or an integer from 1 to 3, R~, R2 and R3 are selected from the group consisting of Cl-C4 alkyl and benzyl, ~;j and R4 is selected from the group consisting of (i(a)) ` CI o C1 8 alkyl, (i(b)) a mono-, di-, or tri-alkyl sub-stituted benzyl, at least one of said alkyl substituents being a C10-Cl~ alkyl group, the other substituent or substituents being Cl-C4 lower alkyl groups, and (i(c)) ;! 30 a mono-, di- or tri-alkyl substituted phenoxy-lower-:1 :

.. . . . .

alkoxy-lower-alkyl radical, said lower-alkoxy and lower-alkyl :~
~: portions having 1 to 3 carbon atoms, said substituents being 1 to 3 calkyl groups having a total of 8 to 12 carbon atoms;

(ii) ~ l5 R5 ~ ;~
~R6-N-R~-NI R6 ) .2X

.~ wherein X is selected from the group consisting of Cl , SO4 , ~ ::
and PO4 , m is an integer from 1 to 3, R5, R6 and R7 are .
selected from the group consisting of Cl-C4 alkyl and benzyl, and R8 is a mono-, di-, or tri-substituted xylylene, at least : one of said substituents being a C10-Cl8 al]cyl group, the other ; substituent or substituents being Cl-C4 lower alkyl groups. ~;
The amount of sodium dichloroisocyanurate dihydrate in the inventive composition can vary over a wide range, for example, ~ ;
: i .~ from 1 to 99% of the composition. The remaining 99 to 1% of the ~:.

~ composition is made up essentially of the quaternary a~monium -~ salt. The preferred composition contains from 65 to 90% by ~ ~.

weight of sodium dichloroisocyanurate dihydrate and from 35 to ~ .
10~ by weight of the quaternary ammonium salt. The optimum composition is one containing about 78% sodium dichloroisocyan~

. urate dihydrate and about 22% quaternary ammonium salt. In :~

.~ addition to the sodium dicloroisocyanurate dihydrate and the :

~ quaternary ammonium salt, the composition may contain from about ~ :~

: ~ ~.01 to about 50% sodium carbonate and other fillers as diatomaceous , ;.
earth and from about .1 to about 5% coloring agents. These ~ 1 .
percents are based on the combined weight of the sodium dichloro~

~ isocyanurate dihydrate and the '. ~ '-,,:. ,: .
.. 30 : ~ :
- ~3~ ~

'.: ;~31 : :

~os~
quaternary ammonium salt in the composiition.
The order of addition of compounds of the inventive composition is not critical. Mixing can take place in most commercially available equipment, provided the mixer employed does not generate excessive heat during mixing.
Mixing apparatuses which do not use a center screw or agitating vane to blend the components of the composition -are particularly desirable. Rotary mixers, for example, tumble type blenders~ which are available are perfectly ~ ;
. ~.
satisfactory. The particle size of components oE the in-ventive composition can be that which is commercially avail~
able. Grinding is generally not desirable since heat or friction developed during grinding may have a deleterious effect on the composition. Suitable particle size is from -10 to -~lQ0 mesh (U. S. Sieve Series ASTM E~ 61)o A wide variety of quaternary ammonium salts is suitable for use in the lnventive composition. Specific examples of quaternary ammonium salts which can be used , ,~ ;include n-alkyl (C~2-C16) dimethylbenzyl ammonium chlorides, ~-. , 20 diisobutylphenoxyethoxyethyldimethylbenzyl ammonium ~ `
chloride monohydrate, methyldodecylbenzyl trimethyl ammonium chloride, n-dialkyl (Cl2-C~) methylbenzyl ammioniumi chlorides, diisobutylcresoxyethoxyethyldimethyl-benzyl ammonium chloride, and methyldodecylxylylene bis(tri-'`I .
- methyl ammonium chloride~. Quaternary ammonium salts in ethanol or ethanol-water solutions can be used, but are not preferred. In most instances, dry compositions possess greater stability and safety. The phosph`ate and sulfate salts of the above quaternary ammonium compounds may be ~i . , ~ 30 used in the inventive composi.tion, however, chloride salts ` : :

~ ~4~
;

0~80 are preferred.
In a further embodiment of the invention, the composition is in the form of a tablet having discrete layers of the sodium dichloroisocyanurate dihydrate and ; the quaternary ammonium salt.
For tablet preparation~ incorporation or application of a mold release agent such as sodium stearate is reco~mended. ~;
Satisfactory pressures for tablet preparation are 1500 to ; 7700 pounds per square inch (p.s.i.)(105.47 to 541.39 kilo~
grams per square centimeter (kg/cm2)). Quaternary ammonium salts in ethanol or ethanol-water solutions are obviously not suitable for use in tablet preparation. f The inventive composition shows distinct advantages over other chlorine releasing agent-organic algaecide compositions in combining significant improvements in safety from fire and ~ i l explosion with long term storage s'ability. The following 'l examples illustrate the present invention. Propor-tionsthrough-out the description and examples are by weight unless other~
:. ~
wise stated.
EXAMæLE I
Separate compositions were prepared containing 10% and 25% by weight, respectively, of the quaternary ammonium chlor-ide, diisobutylphenoxyethoxyethyldimethylbenzyl ammonium chlor-, ide (monohydrate), in combination with 90~ and 75% by weight,i respectively, of a chlorine releasing agent. Four chlorine releasing agents were utilized in preparing separate formula~
tions, namely, sodium dichloroisocyanurate dihydrate, sodium ; dichloroisocyanurate, calcium hypochlorite and calcium hypochlorite dihydrate.
A 20-gauge nichrome wire was bent into a single 18 mm lOS~ 0 diameter loop and the ends of the w~re were connected to a variable transformer. Five grams of the compositions to be tested were placed in a porcelain dish. The nichrome loop was inserted into the center of the mass, the variable transformer ~ ;~
was activated and the current was left on for 5 seconds, during ;
which time the wire glowed red; thereafter the current was . . .
turned off. An electric timer was turned on simultaneously with the variable transformer to measure decomposition time.
Decomposition in the mass being tested was initiated by the hot wire. Decomposition time was measured by the time in seconds required for the decompo~ition to self-; propagate through the entire mass after activation of the variable transformer. In instances where decomposition occurred without insertion of the hot wire, the results were -1 reported as "spontaneous decomposition". Where no self~
i propagating decomposition occurred, after turning off the current, the results are reported as "no decomposition". In comparative Runs S and 6, the self-propagating decompositlon consumed only part of the mass. In those cases, the de-composition time is the time in seconds that elapsed to .,~ , . .
the point where self-propagating decomposition ceased.

Results from this series are set forth in Table I.
, The inventive composition had longer decomposition times, that is, took longer to decompose, than all other compo-sitions with the exception of the compositions used in ;~
comparative Runs 5 and 6. However, the rates of burning for ~; comparative Runs 5 and 6 were faster than the corresponding in~entive Runs A and B and further, the chlorine releasing ag~nt used in Runs 5 and 6 reacts violently with other qua-ternary ammonium salts and has very poor storage stability.

~05~8~
(See Tables II, III, IV, V and VI).
EXAMPLE II
:
Separate compositions were prepared conkaining lO~
and 25~ by weight, respectively, of the quaternary ammonium chloride, n~alkyl (50~ C,.,, 40% C,2, lO~ Clfi) dimethyl-~ , benzyl ammonium chloride (80~ in ethanol), in combination with 90% and 75% by weight, respectively, of a chlorine ,, releasing agent. Five chlorine releasing agents were utilized which include the four used in Example I, plus a ..
fifth, namely, potassium dichloroisocyanurate.
The hot wire tests were performed in a manner i-dentical to that described for F,xample I. Results from this series of tests are set forth in Table II. ~
"': ` ' :~ '. ' '' The inventive composition gave slgnificantly longer decomposition times than all other compo-sitions tested. Inventive Runs C and D had decompo~
sition times of 60 and 77 seconds, respectively.
Comparative Runs ll, 12, 13, 14~ exploded in less than two seconds.
EXAMPLE III
Separate compositions were prepared containing 10% and 25% by weight, respectively, of the quat:ernary ammonium chloride, n-alkyl (50% Cl4, 40~ C,2, 10% C,6) dimethylbenzyl ammonium chloride (50% in solution of 40% water and 10~ ethanol), in combination with 90% and ~ ~ ?
75% by weight, respectively, of a chlorine releasing ~ -~
agent. The chlorine releasing agents utilized were the ; same as in Example I.
The hot wire tests were performed in a manner identical to that described for Example I. Results from ~ ~ ' ~7~ ~ `
' ~

10~88C~
this series of tests are set forth in Table III.
The inventive composition gave significantly better results than all other compositions tested. No decomposition was o~served in the inventive Run F and the decomposition time for inventive Run E was 86 seconds. Compositions used in two of the comparative - runs gave spontaneous decomposition without insertion of the hot wire, namely, Runs 18 and 20. The compo-sition in Comparative Run 17 deflagrated and burned after 16 seconds. Decomposition time for the three remaining comparative runs ranged from 36 to 57 seconds.
EXAMPLE IV
A composition was prepared containing 50~ by weight of the quaternary ammonium chloride, n-alkyl (50~ C 14 40% C 12 1 10% C 16 ) dimethylbenzyl ammonium chloride 80% in ethanol), and 50% by weight of the chlorine releasing agent, sodium dichloroisocyanurate dihydrate.
The hot wire test was performed in a manner identical to that described for Example I. No decomposition was observed for the inventive composition.
i~ :
EXAMPLE V
Separate compositions were prepared containing 4%
by weight of the quaternary ammonium chloride, n-alkyl (93~ C~4, 4% C}2~ 3% C16) dimethylbenzyl ammonium chloride, 95~ assay, in combination with 96~ by weight of a chlorine releasing agent. The chlorine releasing .; ~.
~, agents utilized were, sodium dichloroisocyanurate di-;,, ~i hydrate, sodium dichloroisocyanurate, potassium dichloro-isocyanurate, (monotrichloro) tetra(monopotassium di-chloro) pentaisocyanurate, calcium hypochlorite and cal-'', .

~L0S~88~
cium hypochlorite dihydrate~
These compositions were placed in 23 mm diameter by 65 mm deep clear glass vials covered with permeable polyethylene coated ~one side) Kraft paper, and stored in a 100F(38C)/80% relative humidity oven.

.. ..
Results set forth in Table IV are expressed as the percent available chlorine retention, which was measured after eighteen days. AvaiIable chlorine may be defined as the measure of oxidizing power expressed in terms of elemental chlorine. It is represented hy the ahility of a material to liberate iodine from potassium iodide -~
and is twice the molecular chlorine content.
The inventive composition retained substantially all (94%) of i-ts available chlorine under the3e storage conditions as did the composition used in Comparat~ve ~
Run 22. The remaining comparative examples all showed -~ ;
greater chloxine loss.
EXAMPLE VI
Three series of compositions were prepared using 20 la% by weight of a quaternary ~mmonium chloride in -,.
combination with 90% by weight of a chlorine releasing -~
agent. One of three quaternary ammonium chlorides was chosen for use in each series. The quaternary ammonium chlorides utilized were diisobutylphenoxyethoxyethyl-dimethylbenzyl ammonium chloride monohydrate, n-alkyl (50% Cl4, 40% Clz, 10% Cl6) dimethylbenzyl ammonium chloride (80% in ethanol), and n-alkyl (93~ Cl4, 4% Cl~, 3% C 16 ) dimethylbenzyl ammonium chloride, 95~ assay.
Three chlorine releasing agents were utilized in each 30 series, namely, sodium dichloroisocyanurate dihydrate, ~-_9_ -~.

~SCl ~8~ ~
sodium dichloroisocyanurate and calcium hypochlorite di-hydrate.
Fifteen grams of each composition were placed in a wide mouth 250 ml erlenmeyer flasks, covered with permeable polyethylene coated (one side) Kraft paper and stored for fourteen days in a 100F~38C)/80~ rela-tive humidity oven.
Results set forth in Table V, are expressed as percent available chlorine retention. In each of the three series, the inventive composition retained more available chlorine than all other compositions.
EXAMPLE VII
Separate compositions were prepared containing 10%
by weight of the quaternary ammonium chloride, diiso-butylphenoxyethoxyethyldimethylbenzyl ammonium chloride monohydrate in combination with 90% by weight of a chlorine releasing agent. The chlorine releasing ayents utilized were sodium dichloroisocyanurate dihydrate, ~;
sodium dichloroisocyanurate, and calci~m hypochlorite dihydrate.
.
These compositions were placed in 23 mm diameter by 65 mm deep clear glass vials covered with plastic screw caps and stored at room temperature, 72F to 77F
(22.2C to 25.0C) for eighteen days. Results set forth in Table VI, are expressed as percent available chlorine retention. The inventive composition retained substan-tially all (98.3%) of its available chlorine.
!l , EXAMPLE VIII

Separate compositions were preparèd in the form of tablets having discrete layers of a quaternary ammonium ' ", . . ~ . . . .
: , . . . . . - . . . ...

l~S088~
chloride and a chloxine releasing agent.
Each tablet contains 25% by weight of the `~
quaternary ammonium chloride in combination with 75% by weight of the chlorine releasing agent.
The quaternary ammonium chloride utilized in the preparation of each tablet was either diiso-butylphenoxyethoxyethyldimethylbenzyl ammonium chloride (monohydrate) or n-al~yl (93% C14, 4~ Cl2, 3% C 16 ) dimethylbenzyl ammonium chloride 95% assay.
Two chlorine releasing agents, namely, sodium dichloro-isocyanurate dihydrate and sodium dichloroisocyanurate , -. ~
were utilized individually in combination with each ` i quaternary ammonium chloride.
3.75 g of the quaternary ammonium chloride was poured into a 1.1 inch (2.79 cm.) diameter steel die which had ~; been previously dusted with sodium stearateO 11.25 grams `
` of the chlorine releasing agent was then poured into the die. The die containing the composition was placed in a hydraulic press and 5,200 p.s.i. (365.612 kg/cm2) `~
pressure was applied to form the tablet.
The compositions were pLaced in wide mouth, clear jars covered with permeable polyethylene coated (one side) Kraft paper and stored in a 100F(38C)/80% rela-tive humidity oven for fourteen days. Results set forth in Table VII, are expressed as percent available chlorine retention. In each instance, the inventive run retained a greater percent of available chlorine than the cor-responding comparative run. ~-E AMPLE IX
Separate compositions were prepared in the form of ~`
'' , "

: -11- ~' ,.
.. . .

~5~;;1\880 ~ ~

tablets having discrete layers of the composition com- `~
ponents. Tablets were prepared containing 7% and 93%
by weight, respectively, of the chlorine releasing ;
agent sodium dichloroisocyanurate dihydrate in com-bination with 93~ and 7% by weight, respectively, of a quaternary ammonium chloride. Two quaternary ammonium chlorides, namely, diisobutylphenoxyethoxyethyldimethyl-benzyl ammonium chloride (monohydrate) and n-alkyl (93~ Cl 4, 4% Cl2, 3% Cl 6) dimethylbenzyl ammoniu~
chloride 95% assay, were utilized individually, in com~
bination with 7% and 93% by weight, respe~tively, of ;
the chlorine releasing agent.
Tablets were prepared and stored as set forth above for Example VII. Results set forth in Table VIII, are expressed as percent available chlorine retention.

:

:
;~:~

: :
,:
.' ~, :

.

.' ` ' '~.

.
.
,'` . ~.; :`' .
1:

;:

'''~

~s~
~:
r~ ~_ K
,-1 0 ~ * * IIJ td a~
tn a) ~ O ~ ~ u~ r~ 3 3 ~
O tl~ O O r) ~ cr 1~ ~D t~l ~1 ~, ,~
o 3 .~ .~ .~ ~ -~
E~ u~
o o o :~
o ~ o ~o ui a) ~
. ~ r~ ~ a) 'd ~ ~a ~ ;
. ~ a) ~h ~ ~ ~a t~
~ ~ ~o ~ o o o ,~ o ~a ,~
~, r~ r~
r~ ~ o 1~ h ~
~ ~ ~ hO t~ Q
E~ ~ ~ ~ Q) ~-r~
OO ~-~1 o Ln o In O In o u~
U~ ~ ,~~ r~ ~ r~
O O ,~
C s: ~ ~ h ~a ~a ~hU ~
r--¦. r~ ~¦) td O
_IC) ~1 ~J 3 a) U~ C) ~
~3 X r-l ~1 ~) 3 _~ ~ rl 0O :~ al O O U~ 'd h :~ ~ N ~J ~ C ~ C ~
t~ .a au ~:: 'd OO O O
C Q) ~ ~ rt ~ rl 3 4 1 ~ ~q ~
O ~dO r~ O rl ,a.rl U~ rl U~ ~ i a~ ~ o ~ o o O ~ .~ rl ~ rl ~ -rl ~ h ~ I : C O O O 'd r~ ~ ~ rl ~~ t) P~ C~ (IJ ~ -~ u~ ~ a o ~ ~ o ~ o a~ ..
o a) ~ a~ ~ ~
O ~ O O rl rl S-l~a 'd ,1 C~ ~ U) u~ h ~1 41~ ~1 Sl - :-a) r~ ~1 r~ O O ~0 0 rJ~O O
~ U~ O O r-l r-l ~ao ~, -. r~ h s~ C .c a~ ~ O
~a a) r ~ S C h a) ~ r-~ r l O O r-lh ~ h f~ ~
a) ~ ~ d a),C a~
a rla) rl ~ .rl rC rC ~ 4~1 4~1 a) ~~ ~ ~a ~ ~d o (~
. rl ~ ~¢ ~ r~
. rl F~ J ~) (D~ I ~ ¦ ~d H h ~3 'd ~ rl rl 1~ ~1 a) 1 (1) ~ .~) O rl ~ rl U O ~ C ~I R
a) r-l ~a ~ ~d r-l r-l 'd h u~ u~ o : i h ,C O rl 0 0 al ~ ID rl Q) r~
r~ O U~ ~ ~d ~.r~ ~rl t~
rl t~ r~
O 1~ ~) h C ~ ~ X !t~
U~ ,J ~ ~1 0 ~ O ~ ~
~ a) r-l t) r~l t~ (1 ) ;
'' P; ~ ~ O O O ' a) r~
r ~C m ~ r ~ ~ h ~ h ,,rl (U ~ ~) h :
O E~ h : ~I H ~.) * ~ ~
. :
:

, :
, - . .. . .

~50~80 ~:

~ . Ul Ul U~
.,, ~, o o o o ~Q ~ ,, ,, ,t O ~ o 1~ er ~ ~ ~ ~
~,_ ~ ~ X X X X
O ~ ~ ~ N ~
~ I V V V V '` ~, ~ E~
:~`
,`~ , .
- ' O >10 0 ~.
. . ~ ~ 00 ~,:
'~I I~) N ~1 ~ '. ~`~
O ~ 1 ~,: :
~ ~ U ::
'": U O ~ ,' ~ .
: ~ ~ ~ t) ~t :
(~ b- ` a) o O ~ O ~ O u~ O u^) O ~
~ ~3 U~ ~'. ` '~
:' ~!) ,~ ^ 0~ a) " ':
.,. U') 'I ~ ~ ,.
" ~0 dP--~ ~ rJ ;' ' ' ~

~: ` H O

o ~
E~ ~ ,~ O <~
' 1, : u t~ o o o rl r~
' 1 a~ ~ : i ` ~, ~ rl ~rl O O O
~ ~ .C ,C ;;~
. P; U U
rl ~ E. ~ E~
S~
,: ~ O ~
,........... ~ ~1 ~ ~: ~ ~ Id ~1 ~1 ~ ' .
~-:1 .,1 ~ O-r~ O O ~ ~15 d :>. , ,: , U U~ U : U ~ U ~:: : " , ~,' ,~ o : ' `' '' : 1:: ~ , ~' ~ .~
a E~
H O
.`,, ~.-,' ' ~ ~" ; .
--14 ~ ;~
,: ~ `' '~

~50~313~ ;

a) o-,l o o a r O t~u O r~ 3 ~: O RC~ 1:; 0 O .,1 . ~-,1 .,1~ ~ ~ O
~ rl t) ~ ~ O O ~ ~' ~1 u a ~n ~1 u:~ o ~ Q ~
O 1~ OD ~~1 In ~ o )~ ) o~ o Q~-- E~ ~L) a) O ~ O a) 3 O r~
o a~ o ~ O
Orl ~ o~
l ~ ~ -r aE~ ~ ~ o~ ~ o~
o ~ r-l ~r~ r Z 0 ~ u~ u~ 0 3~
d~ oP ~ .
:~, o o la ,y ,~ 1- 3 :
,~ ,~ ~
~ ~ ` ~ o\
O I N N ~1) ~1~ P ..
~C~ Q)-,l .':
~1~~ ~ . . .
U~O d~ r-l O O r-l ':
OO ~ r-l O
o In O ~ ~ O
I r-l ~I r~
U~ ~ ~ S .`,: -h~ U ~ ,1~ ,~
O o\
~1~1 oP ~ O tO O . ..
~~ ~ ~ ~1 11~ oP ~~ C) ~ rl Rl . ~.

4 l . ~:
o H .1 H O~) al ~
rl - m u~ ~ ~
o ~ U ~ ~ :::
~ O O ~1 h ~ -: s:; s:: m u~ ~ "
O ~1 ~ 1 0 0 : :
O o~
a ~ o o u ~, r~ r~ o o .~ .
Q~ S ~ ~ ~ ~:: -` ~ P~ U U ~ ~ .: ,.
.,. ~ ~ ~.~
., ~ h 1 ~ .rl ~
Hr-l ~ .C ~ ~I r-l ~ -S O-rl O 1~1 td :~ .. ..
''' a) o u~ : o U S , :' ,:~ rl , .
.,1 ~
) !, ~: ' O ":' S~ ~ '''' :' ' ~n :- .:
:~ ~ :-: .': ',':
~ ~ .
;, ~ .~ . :.~ .
1 ~ ~, la Ln ~D 1~ 00 a~ o O ~ .
.:! H C~ .
i'~l; ' . ~' :` .

. .
^: : ` :: : , - : . . : . ` :
~: ~: , . ., . : : :- . , . , , :

~L05~8~
:
.~
~:
oIn o u~
~r~ ~ ~ o r :
, r~ ~ ,, o ~ .
,,,;~

~ r ' :. : rt ~t o ~ u~ ~ ~ ~ o 3 :, o ~ ~
a~ ~ ~ u .:~ h t~ Id 0 0 ~
.,. _lt~ O O O ~ o ,1 .,1 ., ~ ~ ~ tO U~ h O S-l h ~ :
H tiS ~1 ~1 rl O ~J O O O ~:
h U~ O O r~ ^ r~ ~ '-1 . - . ~ .-., ~ ~ d ~1 ~I rC O ~ ~
~ O O O~ l O O U ., m ~ ,~ ,~ ,~ ,t o,~ o ~
o ~ ~ ~: ~ ,~ ~ ~ ~ , p~ U ~ "~
-~t : .,~
1 ~1 ~ o U~
~;1 Q O rl ~ ~rl ~It S~
r-l ~ ,C ~ ~ O ~ ~a ~ t ~1 0 0 E~ 0 ~1 llt u t ~ U~
tr ~ , ~ O .~ ~ .
u:) ~ , ;;

', . `'`
s .,t ~ Id r-l ~ (~) ~ u~

H U
:: :j ',1: '~ , ~,.,: . - ~: , ` ., : :
:, :

1~)S088(~

o .. :`
.,~ .
~ ~.
~ ..
a) a~ :
::
~ ~r; ~, ' .,, o d~~ ^
~ . .~ ., U

I a) ` 0 ~ a N a) X O I ~
'~ ` ~ 00\ '1 0 C~
~1 ~1 ~3 .C ~I o\ N
a) ~~r ~.C
C~ ~1 N a)O O
~ X
.~ O ~
S~ ~ O
O ~ l O ~ .J O -~ ., U~ :>1~1 ,C ~ O
~ ~1 ~ S~ o\ ~ O 5~ o\ ~D ,C `~
O 11~ ~ ~ O O ~ 3 V
.,1 ) >1 (U U~ ~ Q) . ,, ~ ~ 6 ~) ~
~1a) ~ ~ ~ O
O ~ O ~1 ~
QI:i O U~ ~ O h --1 ` N o\ ~I t ) Q
601 ~ rl .~ E3 ~ n~ N ~ O
0 6 ~1 ~ 6 ~ O CO I o\~ F;
., h O ~ h a~ o h O) ~V h ~1 ,, ~ (~ 0 ~ n~td :>~ ,.' 5~ h ~ ~ I h ~ h ~1 O '~' :::, ' : :, m 4~ u t) ~
o ~ o o rl o o rl o o ~
~ 0 0 S~ u) 0 h u~ 0 h ;~, ~1 r~ rl O rl ~ O ~ O
O ~ O ~1 0 0 --I O ~t ,'' -h ~ h ~1 ~1) O O V O O ~ O O U ;, :, rl ~-1 -1 ~I 0 1-1 ~ O ~1 ~I O ,', .,' ~ p; ~ O ~ V t.) ~'I ~.) ~ ~ .'.'" ,' U~ ~ ~ 0 ~ 6 '`
O " ~ 6 h E~
tJ~ h O rl ~ ~ U ~
h ~ ~ ~ ~ ,1 ~d ~ ~ ~1 ~C) ~ ra ,1 ........
O ~ O-rl 0 0 O-rl O ~ O'~l O ~ :~
~n , .
,.
: '' :.
"

:'i rl ~1 0 ~D r`rl H0 OD ~rl 1~ 0 o ~t .' ~ 4 N ~ ~ ~ ~~ ~ 4 ~ ~) i ! ~ 0 ~ ~ p 6 H C.~ H 8 H 8 .
.
,j .
~; ;

: :
.` .
... . .. , . . , , , , :
,, ~.. : . . . `: : . - :, :
. , .. . . . . , . . . : ..

1~5~3~8'~
:: o ~ ~:

:~
, ~:
o ~ ,~
,~ a) a~
s a) : ~
.. ~ , , ; ~:
~ ~ .

. ~ ~ :~
~ ~ ;~ ~-'~Q
o h t 1 ~ ~ >1 ~ $
. ;i H ~:: tr O O rl .. ~ ~3 ~ h !~ w ~ ~ o ~ ; ~:
m ~ ~ o o r~
~:1; 0 ,1 ~ ~1 0 ~-" E~ ~ 1~ : ~
`1 ~ ~ '~
1 ~:
~1 ~1 Q : ~ .
,. ~ ~ ~ ~ ~ ~1 ~' ' ':
:,~ O~1 0 ~ `
a) ~ u~
.. , . ~ ':' ~'.' $ ".~'~`'.;
.. U~ ~`. :' .~ ",`, ~' ' .1 ,: .

.,~
:l ~ ~ ~ ~ ~:.i 1 ~ ~ ~ ~ ;. ,.
::
p ! :
.' :, ,:

:~ ~

o :
~ ~ ~ ~ ~ c~
a ; ,~ o ::
o~o ~ ~ ~

~:
tr~
,1 h rl r~ ;
. ~ ~ ~ ~ h , ~ o,~ O O i ' u~ P~ ~ ut ) ., .
~ a) ~1 ~1 .
~;~` Q ~:: ~~Z
O
~Zj ~ ~ ~ u~

,~ ~ O N Ul I I t~l U~ '`,; . :
1 ~ 1 0 r~
'. I ~ ~ ~ ~ X ~ C~ ~ i`:' ,' ', ' O O >1 d~ ";- ,: "
O ~ Odl N Ln .~ N Ln -X ~~ ~1 ~ X ~
~1 O O ~ l a)-rl .~ ~ ~ 3 U ~ Q ~U.~:: h :.'~ Q ~aJ rl ~r~ ^ ~ O a) ~1 0 ~) O ~;
~ ~u~ ~ 3' Z ~ ~Z ~ Z
Q~ ~ o-~l Q 'd rl h ~ C O X
O ~ O tl~ O N ~ r-l U O U~ ~1 0 ~ ~I C) O
~ ::~ rl ~ s:: O ~ E~ ,1 rC ~j ~ (d ~
U~ ~ F3.,~ Z I '~ F~ ~ "

2 ~ a~
. . .:
.:.:
.~ ' :.
"1: :
~ Z U~

,i:: ` . ,~ æ ,, ~
~
O ., .i'! H U ~ :
:, : 'j ' :~,' :
.` . : , ".`,~ ., -19- . :

:' ` :
.Z

': ~:' '' ; ~ -'.', ': , ~05~)8 o '~
~ ;

o~ o a~ ,~
~ a~ 00 ~ co a~ :
.,, .,, ~ o ~ .: ' .' ~o~) ~', , .:,. ' U~ .
:.
:
E~ O ~ ~
~o 0 ~ ~ ,` ~ ,`
a) ~ ~ a~
~ ~ ~U~
a) ~ ~
H (~ ~ , . .
H ~ 3 0 o O :
I .,~ , m ~ ~ ,~
~1 I a) 0\o ~ o ~
~ rl ~ L >1 . d ~,~ .
.. ~ .~ ~
,~ ~d O O ~
." u~ ~ ~ ,E; ,,, ~o :' ~)i~ ~ ~ ~ ~ o\ ~ ~:
.~ ~ ~ ~ O O ~ ~o O .:
td ~ ~ ~ E~
~ ~ U) O ~ ~ ~ r~
~) 1:~
u~ h O X ~
0 0 N O ~1 ` N
111 ~ o\ ~ ' Ol ~ a) R O : ~: C) R a~ :
., .1 ~:
.3 . U~
, ~ ' ~ ,~ :Z o ~ ~
, .,, H
' ~
~' .

.
:::. , . . . :.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A water-soluble, chlorine releasing compo-sition useful as a sanitizar and algaecide characterized by the following (a) and (b) components, in percent by weight based on the combined weight of (a) and (b):
(a) l to 99% of sodium dichloroisocyanurate dihydrate; and (b) 99 to 1% of a quaternary ammonium salt of the following general formulae, (i) and (ii):

(i) wherein X is selected from the group consisting of C1- , SO4= and PO4? and m is an integer from l to 3, and n is zero or an integer from l to 3, R1, R2 and R3 are selected from the group consisting of C1-C4 alkyl and benzyl, and R4 is selected from the group consisting of (i(a)) C10-C18 alkyl, (i(b)) a mono-, di-, or tri-alkyl substituted benzyl, at least one of said alkyl substituents being a C10-C18 alkyl group, the other substituent or substituents being C1-C4 lower alkyl groups, and (i(c)) a mono-, di- or tri-alkyl substituted phenoxy-lower-alkoxy-lower-alkyl radical, said lower-alkoxy and lower-alkyl portions having l to 3 carbon atoms, said substituents being 1 to 3 alkyl groups having a total of 8 to 12 carbon atoms;

(ii) wherein X is selected from the group consisting of C1- , SI4= and PO4? m is an integer form 1 to 3, R5, R6 and R7 are selected from the group consisting of C1-C4 alkyl and benzyl, and R8 is a mono-, di- or tri-sub-stituted xylylene, at least one of said substituents being a C10-C18 group, the other substituent or substituents being C1-C4 lower alkyl groups.

2. A composition of claim 1 characterized in that sodium dichloroisocyanurate dihydrate is 65 to 90% by weight and the quaternary ammonium salt is 35 to 10%
by weight.

3. A composition of claim 1 characterized in that n is zero, r1 and R2 are methyl, R3 is benzyl, and R4 is a mixed C12-C16 alkyl group.

4. A composition of claim 3 characterized in that R4 is an n-alkyl mixture having 93% C14, 4% C12 and 3% C16, said percents being percent by weight.

5. A composition of claim 3 characterized in that it additionally contains a member selected from the group consisting of water, ethanol and ethanol-water mixtures admixed therewith.

6. A composition of claim 1 characterized in that n is 1, R1 and R2 are methyl, R3 is benzyl and R4 is diisobutylphenoxyethoxyethyl.

7. A composition of claim 1 characterized in that it additionally contains from .01 to 50% of a compound selected from the group of sodium carbonate and diatomaceous earth, said percents being based on the combined weight of the (a) and (b) components.

8. A composition of claim 1 in the form of a tablet comprising discrete layers of the sodium dichloroiso-cyanurate dihydrate and the quaternary ammonium salt.