Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 8~Z9 C 550 (R)
The invention relates to germicidal com~ositions, more
particularly the invention relates to germicidal compositions
based on cationic surfactants suitable for use in dishwashing
and in the cleaning and disinfecting of hard surfaces.
The invention also relates to a method of washing
dishes and general hard surface cleaning utilising such
germicidal compositions.
Liquid detergent compositions, such as are suitable
for use in the manual washing of dishes, are well known
in the art. They are, however~ generally non-germicidal
and are based on synthetic ~nionic detergents to give
them satisfactory foaming properties. For a long time,
however, industrial detergent manufacturers have been
attempting to develop a good quality detergent sanitizer
which would be suitable for manual dishwashing~ etc.,
having the desired properties of combination of Rood
~oaming and cleaning, mildness to the skin, and a
significant reduction of the chance of cross contamination
within the wash solution and an effective sanitization
of the washed surface.
Germicidal dishwashing liquids with foam behaviour
which is inferior to conventional anionic dishwashing
products have been known and on the market for some time.
These are all composed of nonionic detergents with added
quaternary ammonium compounds as germicide and are
generally fairly effective sanitizers but are extremely
poor dishwashing agents. The very low foaming properties,
particularly in the presence of soil and poor wetting, of
"` - 2 - ~
.' ' ' . . . ' ' . ' ' ' ' ' . ' , ,; . ' ' ' . . ' ' ' ~, , ' . '! . . ; .
C 550 (R)
29
nonionic detergents in general are exhibited by such
formulations.
These cationic quaternary ammonium compounds are
low foamers and they cannot normally be formulated With
high foaming anionic surfactants since insoluble com~
plexes are formed between the oppositely charged surfac-
tant ions. Thus nonionic surface-active agents have been
seen as the only real possibility for achieving detergent
properties in the germicidal formulation. The traditional
philosophy has therefore been that a quaternary based
detergent sanitizer must have at least two components
which perform separate functions, i.e. a quaternary
-ammonium compound acting as germicide and a nonlonic
compound as detergent.
The present ~eneration germicidal dishwashing pro-
ducts have to be dosed at hlgh levels in order to get
even the minimum requirements of ~oaming and their;
germicidal effect is reduced by the presence of large
amounts of nonionic substance which tends to lower the
actiVity of the quaternary ammonium compound in solution
by solvation of micelles.
British Patent Specification 1,050,791 describes
~; that water-soluble equimolecular cationic/anionic com-
~; plexes can be made by specific selection of the cationic
and anionic surface-active agents. The cationic used
is a C4-C16 alkyl trimethyl ammonium salt and the an-
` ` ionic surfactant used~has an alkyl or acyl radlca~. of
` _ 3 _
C 550 (R~ ~
a~ 29
from 4 to 16 carbon atoms, the two components being
selected such that the combined total of the carbon atoms
in the cationic alkyl radical and the anionic alkyl radi-
cal is from 18 to 22.
A major drawback of these complexes is, however,
lack of germicidal effect.
A formulation composed of a 1:1 weight ratio of
dodecyl trimethyl ammonium chloride and p-octyl sulpho-
nate was tested and found to give a high foam performance
indeed, but its germicidal effect was very poor under
realistic conditions. Skin irritance tests carried out
with this formulation have also shown that it was very
irritant to the skin. It is llkely that the lack of germi-
cidal activity of this type of formulation can be ex-
plained by the large proportion of anionic, and the
irritancy could also be related to this factor.
Accordingly it is an object of the present inven-
tion to provide a high foam profile to a germicidal
quaternary ammonium compound without substantial loss
of germicidal properties.
It is another object of the present invention
to provide a product based on quaternary ammonium com-
pounds, which exhibits excellent germicidal properties
together with a high foaming behaviour.
Still another object of the invention is to provide
a liquid germicidal cationic detergent composition which
is comparable in foaming behaviour and dishwashing
.
- 4 -
. , .. , , . . ~ . . .... ... .. ..
C 550 (R)
performance with conventional anionic based dishwashing
liquids.
A further object of the invention is to provide
an effective germicidal detergent composition showing
good foam stability in the presence of soil.
A still further object is to provide an improved
formulation for a germicidal dishwashing liquid and for
a disinfecting detergent sanitizer showing a high foaming
behaviour. ~ -
~a It has now been found that the foregoing objects
are attained by combining a specific type-of cationlc
surfactants, as defined hereinafter, with a co-surfac-
tant se~ected from the ~roup consisting of short chain
anionic surfactants having 3-8 carbon atoms in the
hydrophobic group, and low alkoxylated nonionic surfac-
tants having 0-4 ethyIene oxide and/or propylene oxide
groups in the mole`cule, and mixtures thereof.
The cationic surfactant used in the present in-
vention is a quaternary ammonium compound having the -`
formula:
~ R 1 r
L 2
wherein R1 and R2 are each alkyl groups having 9 to 11
carbon atoms; R3 and R~ can each be an alkyl group,
an alkylether group or a hydroxyalkyl group having 1-3
.
5 _
. :
C 550 (R)
P2~
carbon atoms, or a benzyl group; and X is either Cl ,
Br ~ I ~ N03 ~ ~ ~OLI , CH3S04 , C2H5S04 , ~ HP04 or
CH3C00 .
The quaternary ammonium compounds as used in the
present invention are not novel and have been described
in Canadian Patent Specification No. 910,191 and in
Soap ~ Chemical Specialties, March 1969, pages l~7-48/50/
52/86/88/91J92. Though the literature also discloses:the
high tolerance of these quaternary ammonium compounds
~0 to anionic detergents, it was found that compositions
comprising conventional anionic surfactants having more
than 8 carbon atoms in the hydrophobic group or conven-
tional nonionic detergents having morè than 4 ethylene
oxide groups are poor foamers as compared with compositi-
ons of the present invention.
The short chain anionic surfactant may be any of
the organic water-soluble single~ double or triple charged
sulphonates, sulphates, phosphates or carboxylic acid salts,
:~ such as the primary or secondary C3-C8 alkyl sulpho-
nates, sulphates and phosphates, primary or secondary
C3~C8 alkyl ethersulphates having 1-6 ethyleneoxide groups;
~ mono- or di-alkylbenzene sulphonates having 0-2 carbon
'i atoms in the alkyl chain; and natural or synthetic
C3-C8 fatty acid soaps. .
.~ 25 Examples of such short chain anionic surfactants
` are sodium hexyl sulphonate, potassium hexyl sulphonate,
` ammonium heptyl sulphonate, sodlum hexyl sulphate,
-- 6 --
-. - . . : : :. : . :~ . . : : .. ,.: :,.:: . ; : :: :
- : , ,: .,. : ,, :::: :: , : :. , . ... : . :: ., ::,
. :,
.. ., .. .,. ,., : , , .:
~ 9 C 550 (R)
potassium amyl sulphate, ammonium hexyl sulphate, sodium
hexyl phosphàte, potassium butyl phosphate, ammonium
hexyl phosphate, sodium hexyl-3(ethoxy)-sulphate, and
sodium and potassium toluene and xylene sulphonates.
Preferred anionic surfactants are those having 4-7
carbon atoms in the hydrophobic group, the alKall metal
C4-C7 alkyl sulphonates and sulphates such as Na-pentyl
sulphonate, Na-pentyl sulphate, Na-hexyl sulphonate and
Na-hexyl sulphate being particularly preferred.
Suitable nonionic surfactants are those low
alkoxylated nonionics having 0-4 moles of ethylene oxide
and/or propylene oxide per mole, such as the primary or
secondary ethoxylated or propoxylated C8-C16 alkanes
containing 1-4 moles ethylene oxide or propylene oxide
per mole, and the alkyl mono- and diethanolamldes of
carbon chain length ClO~C16. Examples of such~suitable
~: ~ nonionics are coconut fatty acld monoethanolamide, coco-
~ nut fatty acid diethanolamlde, and Cll-C15 secondary
~ alcohol, condensed with 3 ethylene oxide groups, known :
- 20 under the trade name of Tergitol 15-S-3, supplied by
` Union Carbide Corp. ("Tergitol" is a registered trade
mark). ~ :
Accordingly the invention ~rovides a~germicidal
detergent composition comprising essentiall~ an active
mixture of a quaternary ammonium compound having the
` formula:
~ .
7 -
: ` C 550 ~R)
'Zg
, ~
wherein R1 and`R2 are alkyl groups each having 9 to 11
carbon atoms; R3 and RLI can each be an alkyl group, an
alkylether group or a hydroxyalkyl grou~ having 1-3 car-
bon atoms, or a benzyl group; and X is either Cl , Br ,
I- N0 ~ ~ S042 , CH3S04 , C2H5S04 , ~ ~IP 4 3
`and a co-surfactant selected from the group consisting
o~ short chain anionic surfactants having 3-8 carbon atoms
in the hydrophobic group9 low alkoxylated nonionic sur-
factants having 0-ll ethylene oxide and/or propylene oxide
groups in the molecule, and mixtures thereol.
Preferred quaternary ammonium compounds are those
wherein R1 and R2 are alkyl groups of equal chain length
having 9 to 11 carbon atoms; R3 and R4 are each an alkyl
group having 1 to 3 carbon atoms; and X is a halogen
ion.
Examples of suitable auaternary ammonium compounds
0 are:
- dinonyl dimethyl ammonium chloride
didecyl dimethyl ammonium chloride
diundecyl dimethyl ammonium chloride
didecyl diethyl ammonium chloride
didecyl dimethyl ammonium bromide
didecyl dimethyl ammonium iodide
- dinonyl methyl ethyl ammonium chloride.
.
- 8 -
z9 C 550 (R)
Thou~h the ratio of the co-surfactant to the qua-
ternary ammonium compound in the compositions is not
very critical and may vary within a rather wide range, it
will be of advantage to have the co-surfactant in minor
proportions of the quaternary ammonium compound.
Suitable compositions of the invention-will general-
ly comprise an active mixture o~ 30-98 parts by weight
of the quaternary ammonium compound~as deflned above,
0-70 parts by weight of the short chain anlonic co-surfac-
tant as defined above, and 0-25 ~arts by~we~ight of the low
alkoxylated nonionic co-surfactant as deflned above? the
anionic and/or nonionic co-surfactants being present in -~`
at least~5 parts by weight.
~- Preferred compositions are bhose whereln the
- 15 anionic co-surfactant as defined above is~present as the
sole co-surfactant or together with a nonionic co-sur-
.
factant.
~ Hence, in one preferred embodlment of the invention
;~ the composition comprises an active mlxture of 30-98,
preferably 50-95 parts by weight of said quaternary
~ ammonium compound, 5-70, preferably 5-50 parts by weight
;~; of said anionic co-surfactant and 0-25~ preferably 0-20
parts by weight of said nonionic co-surfactant.
Without detracting~from the inventive concept, the
composition may further comprise any of the usual ingre-
dients which could improve consumers' acceptance, e.g.
colouring substances, perfume, etc.
_
C 550 (R)
2~
The composition of the invention may be presented
in any physical form, e.g. as solid particles or prefera-
bly as an aqueous paste or an aqueous liquid solution,
which on use can be diluted to any desirable concentration.
Optimum foaming liquid formulations can be made up
in the form of translucent stable liquids with no added
hydrotropes or non-aqueous solvents. The mixed charge
liquids form structured viscoelastic-systems at active
detergent concentrations as low as a few percent, but
iO are easily pourable up to about 20% active-detergent con-
tent. These aqueous systems can be delivered from a
normal domestic squeeze bottle or by a Venturi pump
tap proportioner. Non-alcohol containing 1lauid compo-
sitions of the invenb`ion can be prepared which are quite
stable over a wide range of~temperatures, preferred con-
centrations being about 10% by weight of total active
detergent components
Examples I-IV
The following four liquid compositions were prepared:
I II III IV
% % % %
Didecyl dimethyl ammonium
chloride 9 9.5 9.2 8
Sodium hexyl sulphonate 1 0.5
Coco-monoethanol amide (CEA)1) - - 0.8
Tergitol ~ 15-S-3 2) - - - 2
Water ~ go 90 90 9O
~ ,. .
-- 10 --
C 55O (R)
CH CH OH
~ 2 2
CEA - C12H25 CON \
H
2) "Tergitol" is a trade-mark of Union Carbide Corporation.
Tergitol 15-S-3 = C11-C15 alkyl-O-(CH2CH2O)3H
- The compositions were tested for germicidal activity.
The germicidal actlvity of the com~ositions was
measured by means of a standard suspension test as des-
cribed below in the presence of 5.4% canteen soiling
(0.4% solids in the solution); 0.05% active material was
used, and also by meana of the more practlcal wash bowl
test.
Standard suspension test for g~ermicidal activity
Test organisms:
Escheria coli ATCC 11229
Pseudomonas aeruginosa ATCC 15442
SalmoneIla typhimurium ATCC 13311
Shigella sonnei ATCC 10014
Experimental:
The tests were carried out at 20C and 40C.
Put 1 ml of the strain suspension including the soil
i.nto a 100 ml Erlenmeyer flask containing the diluted
disinfectant. The dilution of the disinfectant should be
such that the required concentration is obtained with 25
ml of the total test solution.
After a reaction time of 5, 10 and 15 minutes, 1 ml
C 550 (R)
of the liquid is pipetted into 9 ml of inactivating li~uid.
The number of surviving bacteria is then determined in a
suitable agar medium after incubation for 2 days at 32C.
Evaluation:
The bacterial action can be expressed as a log decimal
reduction: No
Germ-killing effect (GE) = Log Nt
N~ = number of bacteria which can be grown before the
disinfectant has acted.
Nt = number of bacteria which can be grown after the
disinfectant has been acting for t minutes. ~-
Canteen soiling: ~0
Protein (albumen) 0.9
Fatty acid (oleic) 0.15
Fat (cooking fat) 2.475
Starch (P 10 X) 3.975
Water ~ to 100.
At 20C all four compositions gave quite sufficient
killing on E.Coli, S.typhimurium and S.sonnei ~GE > 5.0)~
but less killing on P.aeruginosa. At 40C quite sufficient
killing was obtained for all test strains.
The compositions were also tested for their germicidal
activity using a more practical test method as described
below.
Wash bowl test for germicidal activity
Principle:
Soiled stainless steel plates are washed for one minute
- 12 -
C 550 (R)
~Z~ ,
under constant pressure using a rotating brush. Afterwards
the number of surviving bacteria on the plates and in the
wash liquor is determined.
Test organisms:
-
Shigella sonnei
Salmonella typhimurium.
Experimental:
.
Canteen-soiling (see above) is mixed with the test
strain so that there are approximately 107 organisms/g
soiling. 1 g. of this mixture is put on to a stainless
steel plate (4 x 4 cm) and allowed to dry for two hours
at 20C and 70% RH. The plates are then washed, after the
washing of each plate an extra amount ~f 90iling iS added
to the wash liquor (5 g/3 l) to increase the soil level.
After the fifth and tenth plate are washed, a sample
of the wash liquor is taken in order to estimate the
number of bacteria ln it.
To inactivate spores of biocides present on the
plates after washing, each plate is covered with 5 ml
inactivation liquid. After five minutes each plate is put
in a petri dish and 1 ml of the inactivation liquid in
another petri dish and a nutrient is added. The bacteria
are counted after incubation for two daysat 32C.
All four compositions were quite satisfactory in
the wash bowl test.
The compositions were also tested for foam behaviour
in a plate washlng test at a dosage of 0.05% active
- 13 -
.. , . -. -. . . ... ., -
C 550 (R)
detergent using water of 24H. The number of artificiallY
soiled plates that.can be washed in the bowl until ~oam
disappears was recorded. A commercial liquid germicidal
product was used for comparîson.
The following results were obtained: -
Product/composition Plates score Description of product
:,
I 26-28 .
II 22 Compositions of
III 19 the invention
IV 14-17 ~
_ ~ _ _
Laùryl alcohol + 12 ~ . ~
ethylene.oxide 1~.36%J 7 - Co~mercial liquid
. . germicidal product
Lauryl dimethylbenzyl ~
ammonium chloride (6.12%)3
Water 75.52% : ..
. ~ _ ~ ~ '.... '
Example V :
Liquid compositions were prepared containing didecyl
dimethyl ammonium chloride (DDQ) and varying amounts of
sodium hexyl sulphonate (C6S03Na). ~ ~
The compositions were tested for foam behaviour in a
plat~ washing test at a dosage of 0.05% total active
detergent using water of 24H, as described in Examples
I-IV.
.i - 14 -
~ .
, .. , . : . . , . .- ", : .. . ...
C 550 (R)
Compositions Plates score
V1 +,C6SO3Na at 0% of total active -~,~
(DDQ + C6SO3Na) 10
V2 + C SO Na at 1% of total acti~e
56 3 (DDQ + C6SO3Na) 14
V3 + C6SO3Na at 5% of total active
(DDQ + C6S03Na) 22
V4 + C6SO3Na at 10% of total active
(DDQ + C6S03Na) 28
~0V5 ~ C6S03Na at 20% of total active
(DDQ ~ C6SO3Na) 20
Example VI
The foaming behaviour of the following didecyl
dimethyl ammonium chloride/co-surfactant mixtures was
detèrmined in a 500 ml measurir~cylinder with no soil
added, using 100 mls of solutions in demineralised water
at 0~05~ by weight of detergent conc'enkration.
I;o--: , 0~
Co-surfactant Quat./surfactant, Initial After 200 sec.
~ei~ht ratio:
p-hexyl SO3Na 25:1 122 120
Tergitol 15-S-3 1) 1:1 110 110
Tergitol 15-S-9 2) 1:1 110 0
Tergitol 15-S-11 3) 1:1 1~0 25
~5 Tergi,tol 45-S-5 4) 1:1 54 54
Dobanol~25-12 E0 5) 1:1 62 62.
~) C11-C15 alkyl-o(c2H4o)3H suppl~ied by Union Carbide Corp.
2) C11-C15 alkyl-O(C2H4O)gH ~ " " " " "
3) C11-C15 alkyl-(C2H4)llH
3 4) C14-C15 alkyl-O(C2H4O)5H " " " " "
5) C12-C15 alkYl-O(C2H40)12H " Shell Chem. Company.
- 15 -
C 550 (R)
2~
Example VII
- The ~oaming behaviour of the following didecyl
dimethyl ammonium chloride/co-surfactant mixtures was
determined in a 100 ml measuring cylinder wlth ~ravy
soil incrementally added, using 30 mls solution in tap
water at 0.0~5% by weight of detergent concentration.
Co-surfactant Quat./co-surfac- Foam volume(cm3)
tant molar ratio after 2 ml of
soil added
10 p-hexyl SO3Na 4:1 21
p-hexyl SO3Na 1:1 13
Na-xylene sulphonate 1:1 ~ 10
p-decyl SO3Na 1:1 3
. Weight ratio
15 Tergitol 15-S-3 4:1 17
i Lauric acid monoethanol-
amide 3 1 12
Coconut fatty acid mono-
ethanolamide ~:1 19
Dobanol 25-12 EO 1:1 2.
Example VIII
Four commercial sources of didecyl dimethyl ammo-
nium chloride were tested, viz
n ~ :
D a) Onyx BTC 1010 , supplied by the Onyx Company.
25 b) Querto ~210 CL, supplied by the Kemanord Company.
c) Bardac 22 , supplied by Lonza Inc.
d) Dodige ~1881 , supplied by Hoechst.
Results of the p}ate washing test using mixtures
of said quaternary ammoniumcompounds with p-hexyl sulpho-
.
- 16 -
.
C 550 (R)
~ ~ $~J~
nate at 9:1 weight ratio, at a dosage of 0.05% total active
detergent concentration in London water, with standard
gravy soil carried out at 45C are as follows:
~umber of plates washed
Onyx BTC 1010 31
Querton 210 CL 28-29
Bardac 22 26
Dodigen 1881 24
The differences~ althou~h not large, probably indicate
real variations in the effectiveness of the commercial
products as influenced by purity levels.
The superiority of Querton 210 CL to Bardac 22 was
also demonstrated by plate tests on 4:1 mixtures with a
nonionic co-surfactant using the same test-conditions.
Number of plates washed
Querton 210 CL + Tergitol 15-S-3 17
Bardac 22 + Tergitol 15-S-3 14
The four commercial materials were~analysed by Mass
Spectrometry and the ma~n ~mpurities found were the
C8, C10-dialkyl compound and the C10-trialkyl species:
Alkyl chain length Trialkyl Other
C10 (wt%) Cg (wt%)
Onyx BTC 1010 98~ 2
Querton 210 CL 85 15
Bardac 22 75 25 +
Dodigen 1881 100 0 ~ sec. C8-
and C1~
alcohols.
,
- 17 -
C 550 (R)
It appears therefore that the ranking in foam perfor-
mance of the formuiations can be explained in terms of the
impurities detected by this technique. The relative per-
formancesof the first three proaucts correlate sensibly
with the chain length purity of the materials. Dodigen
1881 is composed of dialkyl quaternary which is essential-
ly of just the C10 chain length, however, it does.contain
detectable trialkyl impurities and alcohols which possibly
may act as foam depressants.
No significant differences have been found in the
germicidal effect of these four commercial materials.
: Example IX
Plate washing tests were carried out with the fol-
lowing mixtures. The test conditions were the same as
those used in Example VIII.
Number of plates washed
Querton 210 CL/Na-p-hexyl sul-
phonate (9:1) 28
Querton 210 CL/Na-p-hexyl sul-
phs~e (9:1) 23
Onyx BTC 1010/Na-iso-amyl-
sulp.hate (5:1) 32
Onyx BTC 1010/Na-p-hexyl sul-
phonate (9:1) 31
Onyx BTC 1010/Na-p-pentyl
sulphate (8:1) 30.
Example X
The following liquid compositions were tested for
their germicidal activity using the Quantitative Sus-
- 18 ~
.
, .. ~.
~......... ..
C 550 (R)
2~ :
pension Test published by the Dutch Committee on
Phytopharmacy.
Composition X1 X2 X3 X4
% % %_ % %
Querton 210CL 9 9 9 9 9
Na-butyl sulphate 1 - - - -
Na-pentyl sulphate - 1 - - -
Na-hexyl sulphate
Na-octyl sulphate - - - 1 - .
Na-decyl sulphate - - - - 1
Water 90 90 90 90 90
Principle of the test:
A suspension of the test organism and a solution
of the organic soiling are mixed and then added to the test
solution in such a way that the soil concentration in the
mixture obtained is 0.03% bovine albumen. After a pres- :
cribed contact time at a prescribed temperature the number
of surviving organisms is estimated.
Procedure: .
Mix equal volumes of bacterial or spore suspension
and albumen solution (1.5%).
After 2 minutes 5 add 1 ml of this mixture to the
disinfectant dilution and after 5 minutes, transfer 1 ml
of the disinfectant/organisms mixture into 9 ml of a
universal inactivation liquid at 20C and mix well.
After 5 minutes dilutions are made so that not more than
200 organisms/ml are present and~ if possible, not less
than 20.
- 19 --
."
- C 550 (R)
8~9
~han 20.
Pipet 1 ml of this dilution into a petri dish to prepare
pour plates with 20 ml tryptone-soya-peptone agar melted
and cooled at 43C.
Incubate the petri dishes at 32C (+ 2C) for 48 hours.
Count the number of columns and thus calculate the number
of surviving organisms per ml test solution.
The germicidal effect after 5 min. contact time at
20C are expressed as log decimal reduction (GE).
The results of the tests (average of two tests) are
shown in the following Tables:
- 20 -
C 550 (R)
2~
. o o . l o . .
,:v V ' V ~ V
: :
~r o o oc, ~ o
~: ~ ~ ' .
~ c:) : Lt~ a~ ~ N
~ . ~ ~1 ~' L~\ : ~'
_ _ ' :
~ O Lt~ . ~ ~D a~, .,
X \~ 1~ ~ ~1~ Ir~
_ A ~ A A
~ ~=t o~ ~ ~ ~
- rl ~ . . . ,.
(~I : ~ ~D A Lf~
~ ~ : _ , _
~: ~ ~ . . . : . ~ .
E~ .
~ ~ ~: ~ ~ e
r~ O-rl L~ Lr~ ,L~ U~ .
v ~ ~
: - :
ot~ co co ~D
O
~ ~ ~ ~ , ~ ~ ~
bO ~rl ~ X X X X ~ X
~1 3 ~ ~ ~ ,~ ~ co o ~
r~:l H e~ 1~ t~.i ~ ~ O~ ~
.,0~ U~ _
X Z
H t~ I ~ t~ ~ ~1 O
CC ~: ~ ~ ~ r-l-rl ~1 C~ ~ t~
.. ~; O O ~ ,~ ~ ~ ~ ~ O ~ U~ ~I
u:~ E~ ~ ~ Lr~ cq~ t O ::~ 1~ ~ ~d ~ o
OE-l u~ orl ~1 ~ ^1 ~ E~ ~ ~ D ~ ~1 ~1
C~~ ~ ~0 ~ ~ O r~ S ~ ' ~: C)
p E~ ~ V ~: t~ ~.S ~ ~ a) v ~ ~r-l ~
a). v~ u:~ ~ V O ~ V ~ V ~ > s~ )
~ ~ ~n a) E~ S~ ~ ~ ~ ~
P~: E~ ~ ~d ¢ P~ ~ ¢ I u~ ~ 'C u~ ~ 4 c~ ~ ¢
~ _,
~ :. . :,
-- 21 --
C 550 (R)
~3~2
o o ' o .~ o
V _~v V V
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x v . v .~ ~ ~ ~
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~ o : I ~ .~. ~ .
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X ~ ~o ~ ~ ~D ~
A A `
00 3 Cr~ : L~\ ~\
m I ~ _ ~ o : ^ ~
i~l E ~ E ~ E ~ E
.~o" L~ __ ~\
~ o ,~ E X X X X x . ~
~ ~ O ~I Lr~ ~t a~
~q _ __ ___ ~ ~
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~Z ~ , ~3 C) ~
H ~ 'd N t~ t~l ~ ~1 O ~ ~1 : ' :
cC ~ u~ ~ u~ r-lrl ~ C~ 0
C~ .. P~ O O ~ rl ~ ~ ~ ~ O ~ ~ ~
~ E~ ~ ~ r a) ~ ~ ~ ~ ~ o
O E~ u~ O rl ~ ~ ~ ~ ~ ~ ~ u~ ~ ~ ~d ~.
~ ~ E~ ~ ~~ V ~ ~ V ~ V S ~ ~ r~ V
~n V~ a) ~ V O h V ~ ~ V ~ ~ V ~ V
ul ~ 1~1 tq ~ E-J ~ td ~ E~ ~ :~
P ~; E~ ~ 1~1 ~ 14 E ~ = v~ ~d ¢
. ~ ,
-- 22 --
.
c 550 (~)
' `'`.
~C3 2
._ o o~ , _ _ _ __
~ ~ V V ~ ~
~ o ~ o ~r ~ o . '.
X ~ - v Lr~ m v
-I
X O V . A ~ ~
_ ~ _ _ _ I .`
~ O ~ ~ ~ ~
X ~ '~D ~ C- ~D
_ A A A
S~ 0~ ~ O~` ~0 ~
~ ¦ ~ X 3 _ A _ A
Em~¦ ~ ~ . ~ ~ ~: .~ C
~ .~ Lr~ ~ LS~ ~ ~
V~ _ :
bo~~ ~ ~0 ~0 ~0 ~0 ~ ~0
~ ~ ~ ~ X X X ~1 X
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. _ _ _ ~ __ __ .~
~ U~ C~
X H ~ 1~tl:l ~ ~1 O ~1
¢ '~ u~ ~ ~ ~ ~ c~ cO r~
C~ ..p: O O ~ r~ ~1 ~ ~ O ~\ tq 0~1
u~E~ ~ u~ ~ ~ ~ ~ Lf~ ~
O E-'v~ o rl ~ ~ rl ~ ~ ~ ~1 ~ u7 ~D ~ ~ii
c~ ~ ~ ~0 ~ P 1: o-,l ~ ~ :~ ,~ c)
:~E~ ~ ~ ~ V ~ ~ v ~ ~1 v
v~ a) s~ v I o F~ V r~ ~ ~ ~ V
~,
~: ~ V~ ~ ¢ U~ ~ ¢ _~ ~_,,¢
-- 23 -- .
i~38~29 C 550 (R~
The above results show the overall superiority in
germicidal activity of the compositions X1_XL~ o~ the
invention to composition E outside the invention.
- 24 -
