CA1058071A

CA1058071A - Iodophor disinfectant

Info

Publication number: CA1058071A
Application number: CA240,690A
Authority: CA
Inventors: Philip W. Langford
Original assignee: Tenneco Chemicals Inc
Current assignee: Tenneco Chemicals Inc
Priority date: 1974-11-29
Filing date: 1975-11-28
Publication date: 1979-07-10
Also published as: FR2292429B1; ATA906775A; DE2553956A1; DK538675A; FR2292429A1; CH608965A5; AT352907B; SE7513505L

Abstract

IODOPHORS

ABSTRACT OF THE DISCLOSURE

Improved iodophors, namely iodine-containing compositions having use in combatting bacteria, fungi, viruses and other undesirable micro-organisms, are made in the form of solutions of iodine in tertiary amine oxides. The compositions preferably a liquid medium, which may be water or any monohydric, dihydric or poly-hydric alcohol or mixture thereof, and the iodophor compositions also are preferably made up as acid solutions. Any of a wide variety of surfactants or combinations of surfactants, whether nonionic, cationic or anionic, can form very advantageous components of iodophor compositions. The iodophors can also usefully include soluble iodides, which enhance the available iodine concentrations remarkably. All forms of the compositions are notably stable and effective.

Description

:

:
1al553~7~ ~
.

This invention relates to compositions which are useful in combatting undesirable micro-organisms, including bacteria, f~ngi and virusesO In particular, the invention provides improved iodophors, that is iodine-containing cOmpositions which i.e. have bactericidal, fungicidal and virucidal propertiesO The invention also relates to methods for the preparation of such iodine-containing compositions and also to their application for bactericidal, fungicidal and virucidal purposes and for o~her uses in giving protection from or treatment of undesirable micro-organisms.
The effect of iodine on micro-organisms has long been known and used (see for instance Arch Biochem 6, 261, Wyss, 0. abd Strandskov, FB (1945)). Detergent compositions comprising solutions of free iodine inicertain nonionic surfactants are disclosed in British Patent Specification 703091 (General Aniline ~ Film Corp.), whilst germicidal j'r~; :
i complexes of iodine with (a) quaternary ammonium compounds '~ and (b) phenolethylene oxide condensates are disclosed i,~ ,.
respectively in British Patent Specifications 8256~6 and :::,................................................................... .
'~ 20 9509S4 (~est Laboratories Inc.)r The formulation of iodine-~;` containing surfactant compositions as acid solutions is exemplified by British Patent Specification 962955 (Bendix ' Corp.)~ where the acid used is citric acid~ whilst British : i' ~ Patent Specification 1004282 (West Laboratories IncO) discusses t the stability problems of iodine/surfactant compositions and discloses formulations containing iodine and iodide ionsO
:,,", ,:
~,; i i ~"'''' ~, ; - 2 -, . .
,"~ . ,.

~513~17~
s ' . '' The usefulness of quaternary ammonium compounds for stabili~ing iodophors is recogni~ed in British Patent Specification 1066437 (WOC. Evans ~ Co. (Eccles) Ltdo), which discloses the use of a ,, ~-particular class of nonionic surfactant as the carrier ~; component. Iodine/surfactant compositions are also disclosed in many other publications, including British Patent ~ -Specifications 1167743 (West Laboratories Inc), 1293407 (BASF
Wyandotte Corp) and 1311952 (Marles-Kuhlemann-Wyandotte SA) and iodine/amine compositions are disclosed in British Patent Specifications 1186177 (Diversey Development Ltd.) and 1316571 ~ ~Dipenidum Ltd). ~
:.; .
; It has now been discovered that very useful iodophor compositions can be produced which do not necessarily require ~; the presence of a surfactant or a quanternary ammonium compound and, in particular, that the requisite stability of the iodine-containing compositions can be provided by incorporating in `~ them any of a wide range of tertiary amine oxides.
It has also been discovered generally that compositions ~, having useful properties for bactericidal, fungicidal and -virucidal p~poses and, in general~ for providing protection against infestation by undesirable micro-organisms `~ or for providing treatment of such micro-organisms or of ' objects or locations affected by such infestations can readily be produced from ingredients which are generally readily available, by relatively simple and inexpensive preparative . ~

~
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i 3 ~:'; ,.
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methods.
According to one aspect this invention provides a composition comprising iodine dissolved in a tertiary amine oxide of the general formula , 11 R2 ~ N -wherein Rl, R2 and R3 are the same or different and each represents a sub-stituted or unsubstituted, straight or branched saturated aliphatic, alkoxy, aromatic, aralkyl group or Rl and R2 together with the nitrogen atom form ;` a saturated or unsaturated heterocyclic ring and in the case where the ,.:
;~` heterocyclic ring is unsaturated R is absent.

; 10 According to a further aspect the invention provides a method of manufacture of an iodine-containing composition having bactericidal, fungicidal or virucidal properties or otherwise being useful for combatting undesirable micro-organisms, which comprises dissolving iodine in a tertiary.
, ~` amine oxide of the general formula:
.,, Rl ,, .

R

,-~ wherein Rl, R2 and R3 are the same or different and each represents a sub-,~ stituted or unsubstituted, straight or branched saturated aliphatic, alkoxy, ; aromatic, aralkyl group or any two of Rl, R2 and R3 together with the nitrogen atom form a heterocyclic group.
The tertiary amine oxides selected for making compositions ac-,: :
,~ cording to the invention can have a very wide variety of R substituents, as the~abo~edefinitions of Rl, R2 and R3 show. It has been found that any straight or branched saturated aliphatic or alkoxy groups can be present and . "
that ' ' :

~ - 4 -:.~. ~i, 1051~7~, .
~ these side chains can carry substituents, provided naturally that the sub- ~
.: . .
stituents themselves do not adversely affect the operation of the amine ~`~ oxide structure ~.''.' I .
.'' ~ I
N - O
.', I ':
,. I
,.~ ,, .
in complexing with the iodine in the iodophor composition. In one preferred ~ embodiment of the invention, the tertiary amine oxide is an oxide of a sub-,` stituted or unsubstituted pyridine or quinoline group.
. :
In another preferred embodiment of the invention, the tertiary .7 . ' '.
amine oxide has the formula:

CH

ir !,'j ~ o R N - O
;`,~ I ~`
'!",~ CH3 ~' ,.
in which R represents a substituted or unsubstituted straight or branched saturated aliphatic or alkoxy group or a mixture of such groups and, most preferably, is at least predominantly a C12C14C16C18 ethoxy group- An especially preferred tertiary amine oxide is bis(2-hydroxyethyl)-decylamine i~ oxide.
;~ According to another especially preferable feature of the compo-sitions of the inventiong the iodine-containing composition comprising the tertiary amine oxide, which may itself be constituted by a complex compound ~ or composition, .: ;. j .:~:r ::~
~ .

,, '' '.

.. . .

`:~.: .
`~ 5 :~i 5 .

~C~5~3~7~
is dissolved in a liquid medium. In general~ this liquid medium comprises water, a monohydric, dihydric or polyhydric alcohol or a mixture of any two or more thereof. One preferred class of composition in that in which the liquid medium comprises glycerol or a glycerol-water mixture.
Another preference is for the liquid medium to be water, the composition thus comprising an aqueous solution of the iodine/amine oxide composition.
Another preferred feature of the compositions of the invention is that they comprise acid solutionsO Preferably, sufficient acid is incor-porated that a 1 % aqueous solution of the composition has a pH of 6 or less.
It is especially preferable for the amount of acid incorporated to be such that a 1 % aqueous solution of the composition has a pH in the range from 1 to 4. The compositions preferably include at least one acid sel~ected from hydrochloric, sulphuric, phosphoric, sulphamic, hydroxyacetic and citric acids, though in general any water-soluble acid can be used.
~ A further preferred feature of the iodine-containing compositions ;~ of the invention is that they include at least one nonionic, anionic, or .
cationic surfactant. In general, any surfactant or mixture of such materials can be used, such as form a mutually-compatible composition in accordance ~, with the known state of the art. Thus, one form of surfactant-containing -i,;, ,: :
composition includes a mixture or solution comprising one or more cationic and one or more nonionic surfactants, whilst another form includes a mixture i or solution comprising one or more nonionic and one or more anionic surfac- -;~ tants. An especially preferred surfactant, in general terms, is one which comprises the reaction product of an organic compound having an active hydrogen atom with an alkylene oxide.
Where a nonionic surfactant is included in the compositions, `
: :.
it most preferably is one having the formula " . clOH2l-lCH2cH2 )9 ' A preferred anionic surfactan~ has the formula:
~ 30 cl2H250-(CH2CH20)3-S03Na~
., ~ '~ .

- 6 - ~

... .
. ' , . ' : ' , ' '. . . ' - ' . ': : - :

8~7~L
:
These preferred surfactants exemplify the alkylene oxide reaction products referred to aboveO
Where a cationic surfactant is included in the composition, it most preferably is one having the formula: -.', I . . 14 29 N CH3Br The composition may advantageously also include a water~soluble iodide, for example potassium iodide, which may be added to the composition.
We have discovered that this enables the oxidising properties of the amine oxide to be used to advantage since, by adding a water-soluble iodide to the composition, the amount of available iodine is increased, without impairing ~the stability of the product.
:l An especially preferred iodophor of the invention, useful in com-batting undesirable micro-organisms, comprises the product obtained by dissolving 3 parts by weight of iodine in 17 parts by weight of a nonionic ... . .
surfactant having the formula:
~;i aloH210 - (CH2CH20)9 - H~

i~ adding to the resultant solution S parts by weight of a 30~45% aqueous;:ii~ i solution of bis(2-hydroxyethyl)-decylamine oxide and acidifying the product ;~
by adding a solution of 13 parts ~y weight of sulphuric acid and 8 parts by weight of phosphoric acid in 66 parts by weight of water.
Another preferred iodophor composition comprises the product obtained by dissolving 3.4 parts by weight of iodine in 1906 parts by weight of a 2S%
aqueous solution of a tertiary amine oxide of the formula:
.~,.,~ " .

` R ~ - O

CH
3 ~`
wherein R is predominantly C12Cl~C16C18-ethoxy, and adding to the resultant , . . .
~; :
: ,.
: - 7 -,:-.

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j solution 19.~ parts by weight of a nonionic surfactant of the formula:
,~'i clOH2l -- (CH2CH2 )9 -and acidifying the product by adding a solution comprising 13.3 parts by ~-weight of sulphuric acid and 8.1 parts by weight of phosphoric acid in 36.2 parts by weight of water. The latter composition can be improved further, so as to have a higher available iodine content, by adding 0.4 parts by weight of potassium iodide to 100 parts by weight of the composi-tion per se.
` The invention also provides a method of combatting undesirable ~ ~`
micro-organisms, whether for bactericidal, fungicidal, virucidal or other - purposes, which comprises applying to such micro-organisms or the lo¢us ~ -of treatment thereof an amount of an iodine-containing composition according to the invention as described above.
.i, ~ .
According to a further aspect of the invention~ there is provided a method of manufacture of an iodine- containing composition having : ~ .
; bactericidal, fungicidal or virucidal properties or otherwise being useful. ~ ~ -- .
` for combatting undesirable micro-organisms, which comprises dissolving iodine in a tertiary amine oxide.
Preferably, in one embodiment of this aspect of the invention, ~ 20 the iodine is first dissolved in a surfactant, a solution of the tertiary ?~ amine oxide is then stirred into and admixed with the iodine/surfactant solu-tion and the resultant product is then acidified such that a 1% aqueous solution thereof has a pH of 6 or lessO
: -We have discovered that a composition having particularly effec-tive bactericidal properties in the presence of organic matter may be pre- -~;
pared by the reaction of 0.5-20 parts iodine with 5-50 parts of the sur- -~
factant~ which preferably comprises the reaction product of an organic `

~,. . .
`~ compound having an active hydrogen atom with an aIkylene oxide such as ` 30 ethylene oxide or propylene oxide or mixtures thereof, to which is then ` added 1-30 parts of the selected tertiary amine oxide as stabiliser, pre- ;

ferably~ sufficient acid is then incorporated to lower the pH of a1% dilution :,:..
~:.
i~ ;; - 8 - ~
~,- . ~ .
; . .

5~

of the product in water to 4 or less.
In another preferred embodiment of this aspect of the invention, the iodine is first dissolved in the tertiary amine o.;ide, a cationic, nonionic or anionic surfactant, a composition comprising at least one cationic and at least one nonionic surfactants or a composition comprising at least one nonionic and at least one anionic surfactants is then added to the iodine/amine oxide solution and the resultant product is then acidi-fied such that a I~o aqueous solution thereof has a pH of 6 or less. We have also discovered that a composition having particularly effective bactericidal ;~
t~ 10 and other desirable properties in the presence of organic matter may be pre-; pared by the reaction of 0.5_20 parts iodine with 1-50 parts of the tertiary amine oxide, to which is then added 1-30 parts of a cationic, nonionic or anionic surfactant or any mixture of cationic and nonionic or nonionic and ,., anionic surfactants or a solution thereof~ again preferably with sufficient acid to lower the pH of a l~o aqueous dilution of the resulting product to 6 or less, preferably 4 or less.

In order that the compositions and methods of the present inven-:;
i~ tion may be fully understood and appreciated, the following Examples and test procedures and results are given, by way of illustration.
..... .

~` 3 parts by weight of iodine were added to 17 parts by weight of ! a nonionic surface active agent of the formula ~-,~ C H 0 - (CH CH 03 - H

which had been heated to a temperature of not more than 40 C; the mixture ~ was stirred until dissolution was complete. To the resultant solution, 5 ;~ parts by weight of a 30 - 45% aqueous solution of bis(2-hydroxyethyl)-decylamine oxide were added, with stirring. Finally, a solution of 13 parts i by weight of sulphuric acid and 8 parts by weight of phosphoric acid in . ~ . .
66 parts by weight of water was added, again with stirring. The resultant ,: :
iodophor comprises iodine, a tertiary al~ine oxide and a nonionic surfactant in an aqueous liquid medium formed by a solution of the two mineral acids 1;'., _ 9 _ ;, ' .'~'. ,~
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mentioned.
TEST PROCEDURE AND RESULTS
~hen tested as a general purpose disinfectant by the method of Section 3(i) of the "Exemplary Note of the Appro~al of Disinfectants for the purpose of the Diseases of Animals Act 1950" published by the Ministry of Agriculture, Fisheries and Food, Department of Agriculture and Fisheries ; -~
for Scotland, the composition of Example 1 described above passed at a dilution of 1 part to 180 parts waterO Details of the method are as follows: `-The effective concentration of the disinfectant is that which, -; 4 when added to a yeast organism mixture, gives at least a 10 reduction of ` titre. me Laboratory of the Government Chemist will determine the effective concentration by the following procedure.
The test is made using a 24-hour old culture of Salmonella choleraes~is (N.C.T.C. No. 10653 N.C.I. B. No. 10383) in an Oxoid NoO 2 nutrient broth at 37 + 1 C and containing at least 10 viable organisms per cm . Stock cultures of the test organism are maintained either as ~, .
freeze-dried ampoules or on blood agar base slopes (Oxoid~ bloo~ agar base) and prepared for use in accordance with B.S,S. S08 19380 The working culture is held at an incubation temperature of 37 -~ 1C until just prior to its addition to the yeast suspension. A yeast suspension (5 % dry weight) is prepared according to ~SS.808 1938 and held in cold storage until 4 + 005C
` is reached. The'disinfectant is diluted with sterile 342 ppm hard water HO formula) and reduced ~o a temperature of 4 + 0.5 C.
To 96 cm of the cold yeast suspension, 4 cm of the working culture is added, mixed and dispersed in 2.5 cm portions in an appropriate `
number of 15 x 150 mm Pyrex tubes with metal capsO To each tube is then added 2.5 cm of the appropriate dilution of disinfectant also at 4 + 005C
` and the mixture at once transferred to a fresh cooled tubeO The tubes are held at 4 + 0.5C for 30 minO with shaking at 10 minO intervalsO At the end of 30 min. Ool cm ( 5 drops from a standard 50 dropper) of the mixture is ::: :. .
transferred to 10 cm of nutrient broth (Oxoid No. 2~ containing 5% horse `
` serumO 1 cm at this dilution ( 1 in 100) is added to each of 5 x 9 cm3 ~- Trademark '' -- 10 _ , ,, ; . .
, ,::
,: ,~.
;. .
:. ..
',s' ' ' ' ' ' ' ' ' , ,. . ' , ' . , ' ' ' '., .~:~ . . .
,:: ., , . ;, . . ., : ~ . .

~58~:11'71 nutrient broth (Oxoid No. 2) and incubated at 37 + 1 C for 48 hours. No growth in two or more of five broths = pass. Growth in more than three of five broths = fail.
When tested as a disinfectant for use against tuberculosis by the method of Section 3 (ii) of the same note, the composition described above passed at a dilution of 1 parts to 50 parts waterO Details of this method are as follows:
The effective concentration of the disinfectant is that which, when added to the yeast organism mixture, gives at least a 10 reduction of titre.
me Laboratory of the Government Chemist will determine the effective concentration by the following procedure.
The test is carried out as laid down for general purpose disinfec-tants except that the test organism is a 7-day old culture of Mycobacterium fortuitum (N~C~T~C~ No. 8573 N~CoI~B~ No. 10384), the nutrient broth is Oxoid No. 2 plus 0,05 % Tween~80, the contact time for the yeast-organism and disinfectant mixture is 60 min. at 4 - 005 C and the incubation period 7 days.

., 3.4 Parts by weight of iodine were added to 19.6 parts by weight of Empigen~Y; Empigen~OY is a commercially-av~ilable product and comprises a 25 % aqueous solution of an amine oxide of the formula:

;::

R(OCH2CH2)3 - N - O

-`where R has the following composition % w/w ` 105 - 400 ; C16H33 5 11 ;~ Trademark - 11 -.,~,~

, t : . . , ~' . :. . :, :
.. . . . ...
.'" . ; ., ' ~" ~ :' `~

5i~7~

The Empigen~OY had been heated to a temperature of not more than 40C. To this was then added 1904 parts by weight of a nonionic surface active agent of the form~a CloH2l0~(0C2H4)9~H with stirring. Finally, a solution of 13.3 parts by weight of sulphuric acid and 8.1 parts by weight of phosphoric acid in 36.2 parts by weight of water was added, again with stirring, The resultant iodophor is of the same general type as that of Example lo ., .:`,' ' .
.~ EX~MPLE 3 . 0.4 parts by weight of potassium iodide were stirred into 100 parts by weight of the composition prepared as described in Example 2. The ,.. j 10 available iodine contents of the products of Examples 2 and 3 were determined by titration with standardised sodium thiosulphate solution, with results `~ as follows: Example 2 Example 3 ~:

. hvailable iodine % W/W 2.99 3~20 . When tested as a general purpose disinfectant by the above-detailed method .- of Section 3 (i) of the "Explanatory Notes of the Approval of Disinfectants for the purpose of the Diseases of Animals h~ct, 1950", the compositions .~ ., : described above passed at the following dilutions:

~ E~ - 1 part to 180 parts water .. :
. Example 3 - 1 part to 200 parts water - .

-~. 20 When tested ~s a disinfectant for use against tuberculosis by the method of Section 3 (ii) of the same note, the compositions described above " passed at the following dilutions: ~.
, . . .

Example 2 - 1 part to 90 parts water .. ~ Example 3 - 1 part to lOO parts water : - ~, .
~ hen tested as a disinfectant for use against Foot ~ Mouth Disease . .
~ by the method of Section 3 of the same note, the composition described in ,.. .. ..
; Example 3 passed at a dilution of l part to 300 parts waterO Details of ::

.: this test method are as follows:
- ~. .
- The Animal Virus Research Institute carried out the following j: .
; test: :.

The pH values of the disinfectant in W.H.O hard water containing . . ..
Trademark ': , ~ . . .
. . .
.
: ,. . . :. -:~ C3 5~
.
Eagle's medium ~10%)~' and ox serum (0%, 10% and 50%~ were measured and the concentration of disinfectant estimated at which, in the presence of 50% Ox serum, a 4 log. reduction in virus titre would be obtained (Sellers, 1968). A test was carried out by mi~ing foot-and-mouth disease virus with this concentration of disinfectant in W~HoOo hard water containing 10% ox serumO The mixture was held at 4Co for 30 minutes and then further dilutions made for titrations of residual virus. The concentration under test gave a reduction of at least 104 in virus titreO

, ' ;~ 10 (~Macpherson, I.A. ~ Stoker, H.G.F. (1962). Virology, 16, 147 ~`` Sellers, R.Fo (1968). Vet. Rec. 83~ 504)o When tested as a disinfectant for use against Fowl Test by the method of Section 3 (iv) of the same note, the composition described in Example 3 passed at a dilution of 1 parts to 150 parts water. Details of the method are as follows:
_or use a~ainst Fowl Test (Newcastle disease~_fowl plague)~
;~' The test carried out at the Central Veterinary laboratory at ~ Weybridge, was similar to that laid down for general purpose , ~;, disinfectants except that the test organism was Newcastle disease virus, strain Herts 33. The test mixture was held at 4 C + 0.5C
for 30 minutes and at the end of this time a dilution was made in 5% inactivated horse serumO Further dilutions were made for .~",. ~
~- titration of the virus. The disinfectant under test gave a reduc-~` tion of at least 10 in virus titre.
; ,~ .
In the following Examples 4 to 7 inclusive, the tertiary amine ' oxide was incorporated as a 25% solution of "Empigen OY", as in Example 2 above. The available iodine figures were obtained as described for Examples

2 and 3. Example 4 illustrates an iodophor containing an anionic surfactant, ~:
~`~ Example 5 one containing a cationic surfactant, namely the quaternary ammoni-:i " ~
um compound given, Example 6 one containing both a nonionic surfactant ;.' 7 and a cationic surfactant and Example 7 one containing both an anionic ~ .
surfactant and a nonionic surfactantO
~ ~- Trademark ;; - 13 -: :`

.~`',' ,~ ,. ,, ~

~ ~CI 51~79L

~ EX~MPLE 4 :': 0~96 Iodine Tertiary amine oxide (25% soln) 7~8 -~CH2CH2~3-S03Na (70% soln) 12~0 ... . ..
Orthophosphoric acid 0.4 - -,` Water 78~84 Available iodine: 0.64%
lOO o OO
- :

.. Iodine 1~25 . .
Tertiary amine oxide (25% soln) 11.3 ` Cetyltrimethylammonium chloride (29% soln) 41~5 Orthophosphoric acid 7~5 Sulphuric acid 11 ~ 7 ; Water 26075 ` 100.00 ` Available iodine: 0.60%
~`. EXAMPLE 6 .' Iodine 2.6 ... ..
' Tertiary amine oxide ~25% soln) 1007 CloH2lo-(cH2cH2 )9 10.7 ~ Ben7yl laur~l dimethyl ammonium -:
;, chloride (50~ soln) 41~8 , Orthophosphoric acid 705 ,` Sulphuric aci.d 11~7 .. ,`.` Water 15.0 ;, ~_ , .... ~.~
lOO o O
;..-Available iodine = 2.13%

':'r'~ Iodine 0.96 :~
;................ Tertiary amine oxide (25~o soln) 3.9 ~:~ CloH2lo-(cH2cH2o)9-H 3-9 , - 14- `
.;
:;.;
s, ", ~;i. , . , j ., . . ~ . -; - .

:
~ 6~58~D7 :
E~AMPLE 7 (cont~d) ~, Orthophosphoric acid 0.36 (cH2cH2o)3-so3Na (70% soln) 12.0 ;; Water 78088 ~,~ 100 o 00 ,~
-~ Available iodine 0~81 Using the test procedures already described, the iodophors of Example 4 to 7 were tested in their effectiveness against S. choleraesuis , and M. fortuitum (Ex. 6 and 7 only). Pass results were obtained using 1 part of the iodophor to the amounts of water indicated below.
, . ..
Ex 4 Ex 5 Ex 6 Ex 7 ;; S. chol~aesuis 1/25 1/35 1/80 1/35 ;.
M. fortuitum 1/20 1/20 1/100 1/20 Amine Oxide (substituted aliphatic) ~, Iodine 2a45 . ~ .
C12C14C16C18 ethoxy dimethyl amine oxide ~' (25% solution) 66.0 Orthophosphoric acid 1075 2_Propanol 29.8 '`'.' 100.00 ''.
. ` .
Available iodine 1.73% `-Pass dilution ($. choleraesuis) 1/30 " " (M. fortuitum) 1/80 ., ~
~' EXAMPLE 9 ~- Amine oxide (Heterocyc~ic) Iodine 1.66 . . . j . .
Pyridine-l-oxide 16.6 2-Propanol 40.0 ',',;'!' Orthophosphoric acid 005 ~ Water 41.24 ; . ;. - :
00.00 ,;" ' '~,' ' '"
, ~5~i[3 7:~L
.. ..

~ EXAMPLE 9 continued ., .
Available iodine 1. 61~o Pass dilution (S. choleraesuis) 1/60 M. fortuitum) l/loo Example 10 ` Nonioni~Amine oxide (comparison) (A) (B) Iodine 5 5 -H210~(0C2H4)9~H 22.5 22.5 , clo-l2H2l-25o-(oc2H4)5-H 5~5 5~5 `
Dimethylcoco amine oxide (40%) 15~6 (Aromox~'DMCD~ Armour Hess Chemicals Ltd) Bis(2-hydroxyethyl)cocamine oxide) - 15~6 ,~ (Aromox C/12, Armour Hess Chemicals Ltd) i~ Orthophosphoric acid 9.3 9.3 ~ Sulphuric acid 15.0 15.0 ; Water 27.1 27.1 " 100~0 lOOoO
~; (A) (B) ;

Available iodine % 3.81 3054 , Pass dilution (S. choleraesuis) 1/200 1/200 ;;
~!` 1l n (M. fortuitum) 1~20 1/120 ~ EXAMPLE 11 Anionic/Am e oxide . Iodine Q~95 ~, C C C C ethoxy dimethyl amine oxide 7.9 12 14 16 18(25% SOlution) ",.,~ ,.
Dodecyl benzene sulphonic acid 8.4 Orthophosphoric acid 003S
,` 2-Propanol 16~0 `'~ Water 66~4 `'~,"' 100.00 Available iodine 0.85%
Trademark 16 - ;
:". ,; , .
.j .,,~, . ;:

~CI 51~3~7~

EXAMPLE 11 continued Pass dilution (S. choleraesuis) 1/50 c~ :
" " (M. fortuitum~ 1/35 .: EXAMPLE 12 .
Nonionic/Amine oxide with ~lycerol : Iodine 2.5 CloH2lo-(oc2H4)9 11.3 ClO 12H21-25 (C2 4)5 3.1 C12C14C16C18 ethoxy dimethylamine oxide14.4 HI (50% solution) 0.4 Orthophosphoric acid 2.4 . . .
. Glycerol 40.0 . Water 23.9 , :
'` 100.0 . Available iodine 2.3%
' Pass dilution (S. choleraesuis) 1/110 .~ " " (M. fortuitum) 1/7S
: EXAMPLE 13 -;~ onionic!Amine oxide (Aromatic) .: :
~ 20 Iodine 4-7~ i ;: CloH2lo-(oc2 4)9 21.3 ,...................................................................... . .
C10 12H21 250-(OC2H4)5-H 5 4 . Benzyldimethyl amine oxide (30% solution) 1908 ~:
;. Orthophosphoric acid 8.8 ~
, ~ :
, Sulphuric acid 14.3 .... .
Water 25.65 `'`` 100.00 ;,, ... .
~; Available iodine 4.2%
;.
Pass dilution (SO choleraesuis) 1/250 ~
. . ~ . .
~` " " (M~ fortuitum) 1/140 : .
.,~. i: . .
',.~' , -,:
:~ - 17 -,'.' :

j; .....

- \ ~
~C~5~3~17~
:, EX~MPLE 14 .
Nonionic (ethoxylated alkyl phenoly~mine oxide Iodine 2.85 CgHl9c6H40-(oc2H4)l2 14.15 C C14C16C18ethoxy dimethylamine oxide 13~25 :
(25% solution) Orthophosphoric acid 8.0 .. ~ Sulphuric acid 13.0 Water 48.75 100.00 , .
Available iodine 2015%
. 10 Pass dilution (S, choleraesuis) 1/90 " " (M. fortuitum) 1/60 ~:

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.,.

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,~ '', . i , .~.... ~ .

~ .. .. .

~, ' ' :

'". :: : ' i .... . .

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.~, ',~ ' .

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition comprising iodine dissolved in a tertiary amine oxide of the general formula:

wherein R1, R2 and R3 are the same or different and each represents a sub-stituted or unsubstituted, straight or branched saturated aliphatic, alkoxy, aromatic, aralkyl group or R1 and R2 together with the nitrogen atom form a saturated or unsaturated heterocyclic ring and in the case where the hetero-cyclic ring is unsaturated R3 is absent.

2. A composition according to claim 1, wherein the tertiary amine oxide is an oxide of a substituted or unsubstituted pyridine or quinoline group.

3. A composition according to claim 1, wherein the tertiary amine oxide has the general formula:

wherein R represents a substituted or unsubstituted, straight or branched saturated aliphatic or alkoxy group or a mixture of such groups.

4. A composition according to claim 3, wherein R represents a C12C14C16C18-ethoxy group.

5. A composition according to claim 1, wherein the tertiary amine oxide is bis(2-hydroxyethyl)-decylamine oxide.

6. A composition according to claim 1, 2 or 3 which is dissolved in a liquid medium comprising water, a monohydric, dihydric or polyhydric alcohol or a mixture of any two or more thereof.

7. A composition according to claim 1, 2 or 3 which is dissolved in a liquid medium which comprises glycerol or a glycerol-water mixture.

8. A composition according to claim 1, 2 or 3 which comprises an aqueous solution.

9. A composition according to claim 1, 2 or 3 which comprises an acid solution.

10. A composition according to claim 1, 2 or 3 which includes sufficient acid that a 1% aqueous solution of the composition has a pH of 6 or less.

11. A composition according to claim 1, 2 or 3 which includes sufficient acid that a 1% aqueous solution of the composition has a pH in the range from 1 to 4.

12. A composition according to claim 1, 2 or 3 which comprises an aqueous solution containing at least one water-soluble acid in sufficient quantity that a 1% aqueous solution of the composition has a pH of 6 or less.

13. A composition according to claim 1, 2 or 3 which includes at least one acid selected from hydrochloric acid, sulphuric acid, phosphoric acid, sulphamic acid, hydroxyacetic acid and citric acid.

14. A composition according to claim 1, 2 or 3 which includes at least one nonionic, anionic or cationic surfactant.

15. A composition according to claim 1, 2 or 3 which includes a mixture or solution comprising one or more cationic and one or more nonionic surfactants.

16. A composition according to claim 1, 2 or 3 which includes a mixture or solution comprising one or more nonionic and one or more anionic surfactants.

17. A composition according to claim 1, 2 or 3 which includes a mixture or solution comprising a nonionic and one or more cationic or anionic surfactants and wherein the nonionic surfactant has the formula:

C10H21O-(CH2CH2O)9-H.

18. A composition according to claim 1, 2 or 3 which includes a mixture or solution comprising one or more nonionic and a cationic surfactant, wherein the cationic surfactant has the formula:

19. A composition according to claim 1, 2 or 3 which includes a mixture or solution comprising one or more nonionic surfactants and an anionic surfactant, wherein the anionic surfactant has the formula:

C12H25O-(CH2CH2O)3-SO3Na.

20. A composition according to claim 1, 2 or 3, wherein the composition comprises a nonionic surfactant which is the reaction product of an organic compound having an active hydrogen atom with an alkylene oxide.

21. A composition according to claim 1, 2 or 3 which includes at least one water-soluble iodide.

22. A composition according to claim 1, 2 or 3 which includes potassium iodide.

23. An iodine-containing composition useful in combatting undesirable micro-organisms, which comprises the product obtained by dissolving 3 parts by weight of iodine in 17 parts by weight of a nonionic surfactant having the formula:

C10H21O-(CH2CH2O)9-H, adding to the resultant solution 5 parts by weight of a 30%-45% aqueous solution of bis(2-hydroxyethyl)-decylamine oxide and acidifying the product by adding a solution of 13 parts by weight of sulphuric acid and 8 parts by weight of phosphoric acid in 66 parts by weight of water.

24. An iodine-containing composition useful in combatting undesirable micro-organisms, which comprises the product obtained by dissolving 3.4 parts by weight of iodine in 19.6 parts by weight of a 25% aqueous solution of a tertiary amine oxide of the formula:

wherein R is predominantly C12C14C16C18-ethoxy, and adding to the resultant solution 19.4 parts by weight of a nonionic surfactant of the formula:

C10H21O-(CH2CH 2O)9-H

and acidifying the product by adding a solution comprising 13.3 parts by weight of sulphuric acid and 8.1 parts by weight of phosphoric acid in 36.2 parts by weight of water.

25. An iodine-containing composition useful in combatting undesirable micro-organisms, which comprises the product obtained by adding 0.4 parts by weight of potassium iodide to 100 parts by weight of the composition defined by the claim 24.

26. In an iodophor composition comprising iodine dissolved in at least one surfactant selected from the group consisting of nonionic surfactants, anionic surfactants and quaternary ammonium cationic surfactants, an acid selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, sulfamic acid, hydroxyacetic acid, citric acid and mixtures thereof, and a liquid medium selected from the group consisting of water, monohydric alcohols, dihydric alcohols, polyhydric alcohols, and mixtures thereof, the improvement which comprises incorporating in said composition an amount sufficient to increase the biocidal activity of said composition of at least one tertiary amine oxide of the general formula where R is an alkyl group having from about 10 to about 18 carbon atoms and mixtures thereof, and n is an integer from 0 to 4.

27. A composition according to claim 1 wherein the tertiary amine oxide is pyridine N-oxide.

28. A composition according to claim 1 wherein the tertiary amine oxide is N,N-dimethyl benzylamine N-oxide.

29. A composition according to claim 1 wherein the tertiary amine oxide is N,N-dimethylcocoamine N-oxide.

30. A composition according to claim 1 wherein the tertiary amine oxide is of the formula:

where R has the following composition % w/w C10H21 1.5 - 4.0

31. A composition according to claim 2 wherein the tertiary amine oxide is an oxide of an unsubstituted pyridine or quinoline group.

32. A method of combatting undesirable micro-organisms, which com-prises applying to such micro-organisms or the locus of treatment thereof an amount of an iodine-containing composition as defined in claim 1, 2 or 3.

33. A method of manufacture of an iodine-containing composition hav-ing bactericidal, fungicidal or virucidal properties or otherwise being useful for combatting undesirable micro-organisms, which comprises dissolv-ing iodine in a tertiary amine oxide of the general formula:

wherein R1, R2 and R3 are the same or different and each represents a sub-stituted or unsubstituted, straight or branched saturated aliphatic, alkoxy, aromatic, aralkyl group or any two of R1, R2 and R3 together with the nitro-gen atom form a heterocyclic group.

34. A method according to claim 33, wherein the iodine is first dis-solved in a surfactant, a solution of the tertiary amine oxide is then stir-red into and admixed with the iodine/surfactant solution and the resultant product is then acidified such that a 1% aqueous solution thereof has a pH
of 6 or less.

35. A method according to claim 34, wherein 0.5-20 parts of iodine are reacted with 5-50 parts of the sufactant and then 1-30 parts of the tertiary amine oxide are added.

36. A method according to claim 33, wherein the iodine is first dis-solved in the tertiary amine oxide, a cationic, nonionic or anionic surfact-ant, a composition comprising at least one cationic and at least one nonionic surfactant or a composition comprising at least one nonionic and at least one anionic surfactant is then added to the iodine/amine oxide solution and the resultant product is then acidified such that a 1% aqueous solution thereof has a pH of 6 or less.

37. A method according to claim 34, wherein 0.5-20 parts of iodine are reacted with 1-50 parts of the tertiary amine oxide and 1-30 parts of at least one surfactant or surfactant composition are then added.

38. A method according to any of claims 33, 34 or 35, wherein at least one water-soluble iodide is incorporated into the composition.

39. A method according to any of claims 34, 35 or 36, wherein acidifi-cation is effected by adding an aqueous solution of sulphuric and phosphoric acids.

40. A composition according to claim 2 wherein the tertiary amine oxide is an oxide of an unsubstituted pyridine or quinoline ring.