CA1127076A - Germicidal iodine compositions with enhanced iodine stability - Google Patents
Germicidal iodine compositions with enhanced iodine stabilityInfo
- Publication number
- CA1127076A CA1127076A CA360,395A CA360395A CA1127076A CA 1127076 A CA1127076 A CA 1127076A CA 360395 A CA360395 A CA 360395A CA 1127076 A CA1127076 A CA 1127076A
- Authority
- CA
- Canada
- Prior art keywords
- iodine
- composition
- germicidal
- range
- compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/12—Iodine, e.g. iodophors; Compounds thereof
Abstract
GERMICIDAL IODINE COMPOSITIONS
WITH ENHANCED IODINE STABILITY
Abstract of the Disclosure New and improved germicidal iodine compositions are provided in which iodine levels, in the presence of organic adjuvants containing at least carbon, hydrogen and oxygen atoms, are maintained for extended periods of time in the presence of iodide, through the addition of iodate and control of pH within the range of pH 5-7.
S P E C I F I C A T I O N
WITH ENHANCED IODINE STABILITY
Abstract of the Disclosure New and improved germicidal iodine compositions are provided in which iodine levels, in the presence of organic adjuvants containing at least carbon, hydrogen and oxygen atoms, are maintained for extended periods of time in the presence of iodide, through the addition of iodate and control of pH within the range of pH 5-7.
S P E C I F I C A T I O N
Description
~ 7~6 This invention relates to new and improved iodine germicidal compositions in which iodine levels, in the presence of organic adjuvants containing at least carbon, hydrogen, and oxygen atoms, are maintained over a period of tirne in the pres-ence of iodide, through the addition of iodate and pH maintenance in the range of pH 5-7.
The purpose of this invention is to provide iodine compositions of greatly increased elemental iodine stability on storage, where the elemental iodine is formulated with adjuvants such as organic detergents, solvents, foam stabilizers, thick-eners, buffering agents or the like, that contain carbon, hydrogen, and oxygen atoms (and which may also contain other atoms such as nitrogen, phosphorus, sulfur, etc.). In such compositions the elemental iodine concentration almost always decreases on storage, frequently decreasing much beyond the acceptable amounts allowed ~or labelling purposes. This inven-tion teaches how the elemental iodine levels can be maintained by the addition of iodate and maintaining the pH in the range of pH 5-7. This teaching is particularly valuable in situations where it is desirable to maintain elemental iodine at levels below 1~, and as low as about 0.01~.
The detergent-iodine literature, mostly consisting of patents and product labels, contains many examples of germi-cïdal iodine products containing 0.5 to 20% iodine~ There are hardly any instances of iodine products containing only 0 1~
iodine or less. There are two very good reasons for this gap.
The first reason is that almost all iodine products of~ered ~, .
1~7~7~
for sale are in reality concentrates of one type or another.
The directions for use ordinarily call for dilution with water, --usually dilutions in the range of l:lO0 to l:lO00 ~1ith wa~er, so as to provide anywhere from a few ppm of titratable iodine to perhaps 150 ppm iodine at the use-dilution After use, the diluted product is discarded, since the iodine content of the dilution is only-stable for hours, not for weeks or months.
For any product intended to be used after dilution with water, it pays to make the product iodine level concentrated, rather than dilute~ so that the product is "economical" in view of the final use, in order to compete with other germicidal substances.
The second reason that detergent-iodine products rarely contain O.l~ iodine or less is that it was and is (until now) virtually impossible to maintain a guaranteed amount of iodine at such a low level. For example, a typical iodine product with a label statement guaranteeing 1.6~ iodine will ordinarily contain about 1.8~ iodine or more when it is manu-factured, and it may drop to as low as 1.5~ iadine two years after it was manufactured. If the same product, with the same detergent content were prepared with only O.l~ iodine at the start, the iodine content would probably drop to 0~ within a few weeks,--certainly within a few months~ through slow reaction of the iodine with the organic components of tne formulation.
There are certain types of iodine products which are ordinarily not diluted prior to use --such as hand washing compositions, bovine teat dip products to prevent mastitis, and roducts ~or topical application Such products ~req~1ently .' 07~i . .
do not require high iodine content for e~fectiveness~ yet ~ormu-lators find that they have to put in much more than is needed so that the iodine that is lost is an acceptable arnount ba~e~
on the percentage o~ loss relative to the amount speci~ied on the label. For example, if the organic constituents o~ an iodine product will react with about 0.2~ iodine over the shel~
life of the product, and if E P.A. or F~DoA~ label requirements dictate that the product have no more than 110%, and no léss than 90~ of the labelled amount of iodine active ingredient, then a formulator is forced to set the labelled iodine level at no less than 1.0~, since only then could he manufacture at 1.10~, and end up as low as 0.90~ at the end of the guaranteed shelf li~e, a 0.2~ drop in iodine content, while remaining within the regulatory agency requirements. In reality the 1~
iodine in the product could be ten times or more iodine than is necessary for the purpose o~ ef~icacy.
In the case of the bovine teat dip, the extra iodine, over what is needed for ef~icacy, is a problem in that it needlessly contributes to iodine levels in milk through skin absorption or through improper teat washing be~ore milking.
In the case of a hand washing composition, the extra iodine contributes to unattractive color, attacks jewelry (rings, etc ) on the hands, and frequently leaves a te~porary yellow color on the skin.
It is well known that iodate and iodide react in the presence of hydrogen ions to yield elemental iodine and water according to the equation:
_4_ 11~7~
I03 + 5I + 6H ~ ~ 3I2 + 3H20 It is also well known that this reaction is ver~J ~ast at low pH, e g. pH 1, 2, or even ~, and that it is slowed down at high~r pH values, becoming almost non-reactive at pH 7 and above Certain dry compositions containing an iodate, an iodide and-excess solid acid have been proposed as a means of providing iodine itself at the time of solution in water. The purpose of this invention is to use this reaction to provide very slow release of iodine -- so slow that it has never been used before for this purpose -- to counterbalance the slow loss of iodine in iodine compositions that contain organic water soluble substances.
The compositions of this invention contain elemental iodine in an amount that usually does not exceed 1~, but is more generally in the.range of 0 01~ to 0.25~ iodine, iodide ion (from any source) p~eferably in the range of 0.05~ to 0.5~;
iodate ion (from any source), a.t least 0~005~ preferably in the range of 0.05~ to 0.1~, an organic substance or substances (detergent or soivent, for example) which contains C, H, and 0 atoms in an amount from 1 to 50~, and pH control, usually accomplished by the inclusion o~ a buffering agent (citra~e, phosphate, etc.) capable of maintaining a pH in the range of 5 to 7.
The maintenance of the pH in the narrow range of 5 to 7 is the essence, since below pH 5, the reaction of iodate and iodide has been ~ound to proceed too fast to be of value 'I
for the purpose of this invention and would generate iodine faster than necessary, resulting in too high an elemental iodine level, too rapid depletion of iodate, and ultim~tely no counterbalance of iodine loss through iodine regenera~ion The range o~ iodide concentration oP this invention is not characterized by sharp limits. The lower pre~erred -range limit of 0 05~ represents an amount which ordinarily must be present in order to provide a sufficient amount to react with the iodate. The upper preferred limit.provides both a large "reservoir" to be drawn ~rom, and the higher concentra-tion necessary whën large amounts o~ iodine have to be replen-ished, or with higher buf~ered pH, closer to pH 7, when a higher iodide concentration is desired to increase the rate o~ iodine formation The range of iodate ion, from any source, should start at about 0.005%, so that it can provide~ ultimately about 0 02~
.extra iodine in a ~ormulation. For most practical applications, an amount of 0.05 - 0.1~ can be used. Higher amounts can be used, dictated by e ~nomics.
The organic substance is an integral part of this invention in that all the uses contemplated concern maintaining the concentration o~ elemental iodine in an aqueous medium con-taining organic substances suc~h as a solvent, an iodine solu-bilizer~ an iodine complexing agent, etc., detergent~ or the like. Elemental iodine reacts more or less with all such organic substances which contain carbon, hydrogen, and oxygen ("C, N, nd 0"). Unless such C, H, 0 containing substance is .' ' .
.
~- I q~27~76 present, there is no need ~or this invention This inventio~
is applicable to essentially all previous aqueous "comple~e~
iodine" art typified b~ the subject matter in U S, Patents
The purpose of this invention is to provide iodine compositions of greatly increased elemental iodine stability on storage, where the elemental iodine is formulated with adjuvants such as organic detergents, solvents, foam stabilizers, thick-eners, buffering agents or the like, that contain carbon, hydrogen, and oxygen atoms (and which may also contain other atoms such as nitrogen, phosphorus, sulfur, etc.). In such compositions the elemental iodine concentration almost always decreases on storage, frequently decreasing much beyond the acceptable amounts allowed ~or labelling purposes. This inven-tion teaches how the elemental iodine levels can be maintained by the addition of iodate and maintaining the pH in the range of pH 5-7. This teaching is particularly valuable in situations where it is desirable to maintain elemental iodine at levels below 1~, and as low as about 0.01~.
The detergent-iodine literature, mostly consisting of patents and product labels, contains many examples of germi-cïdal iodine products containing 0.5 to 20% iodine~ There are hardly any instances of iodine products containing only 0 1~
iodine or less. There are two very good reasons for this gap.
The first reason is that almost all iodine products of~ered ~, .
1~7~7~
for sale are in reality concentrates of one type or another.
The directions for use ordinarily call for dilution with water, --usually dilutions in the range of l:lO0 to l:lO00 ~1ith wa~er, so as to provide anywhere from a few ppm of titratable iodine to perhaps 150 ppm iodine at the use-dilution After use, the diluted product is discarded, since the iodine content of the dilution is only-stable for hours, not for weeks or months.
For any product intended to be used after dilution with water, it pays to make the product iodine level concentrated, rather than dilute~ so that the product is "economical" in view of the final use, in order to compete with other germicidal substances.
The second reason that detergent-iodine products rarely contain O.l~ iodine or less is that it was and is (until now) virtually impossible to maintain a guaranteed amount of iodine at such a low level. For example, a typical iodine product with a label statement guaranteeing 1.6~ iodine will ordinarily contain about 1.8~ iodine or more when it is manu-factured, and it may drop to as low as 1.5~ iadine two years after it was manufactured. If the same product, with the same detergent content were prepared with only O.l~ iodine at the start, the iodine content would probably drop to 0~ within a few weeks,--certainly within a few months~ through slow reaction of the iodine with the organic components of tne formulation.
There are certain types of iodine products which are ordinarily not diluted prior to use --such as hand washing compositions, bovine teat dip products to prevent mastitis, and roducts ~or topical application Such products ~req~1ently .' 07~i . .
do not require high iodine content for e~fectiveness~ yet ~ormu-lators find that they have to put in much more than is needed so that the iodine that is lost is an acceptable arnount ba~e~
on the percentage o~ loss relative to the amount speci~ied on the label. For example, if the organic constituents o~ an iodine product will react with about 0.2~ iodine over the shel~
life of the product, and if E P.A. or F~DoA~ label requirements dictate that the product have no more than 110%, and no léss than 90~ of the labelled amount of iodine active ingredient, then a formulator is forced to set the labelled iodine level at no less than 1.0~, since only then could he manufacture at 1.10~, and end up as low as 0.90~ at the end of the guaranteed shelf li~e, a 0.2~ drop in iodine content, while remaining within the regulatory agency requirements. In reality the 1~
iodine in the product could be ten times or more iodine than is necessary for the purpose o~ ef~icacy.
In the case of the bovine teat dip, the extra iodine, over what is needed for ef~icacy, is a problem in that it needlessly contributes to iodine levels in milk through skin absorption or through improper teat washing be~ore milking.
In the case of a hand washing composition, the extra iodine contributes to unattractive color, attacks jewelry (rings, etc ) on the hands, and frequently leaves a te~porary yellow color on the skin.
It is well known that iodate and iodide react in the presence of hydrogen ions to yield elemental iodine and water according to the equation:
_4_ 11~7~
I03 + 5I + 6H ~ ~ 3I2 + 3H20 It is also well known that this reaction is ver~J ~ast at low pH, e g. pH 1, 2, or even ~, and that it is slowed down at high~r pH values, becoming almost non-reactive at pH 7 and above Certain dry compositions containing an iodate, an iodide and-excess solid acid have been proposed as a means of providing iodine itself at the time of solution in water. The purpose of this invention is to use this reaction to provide very slow release of iodine -- so slow that it has never been used before for this purpose -- to counterbalance the slow loss of iodine in iodine compositions that contain organic water soluble substances.
The compositions of this invention contain elemental iodine in an amount that usually does not exceed 1~, but is more generally in the.range of 0 01~ to 0.25~ iodine, iodide ion (from any source) p~eferably in the range of 0.05~ to 0.5~;
iodate ion (from any source), a.t least 0~005~ preferably in the range of 0.05~ to 0.1~, an organic substance or substances (detergent or soivent, for example) which contains C, H, and 0 atoms in an amount from 1 to 50~, and pH control, usually accomplished by the inclusion o~ a buffering agent (citra~e, phosphate, etc.) capable of maintaining a pH in the range of 5 to 7.
The maintenance of the pH in the narrow range of 5 to 7 is the essence, since below pH 5, the reaction of iodate and iodide has been ~ound to proceed too fast to be of value 'I
for the purpose of this invention and would generate iodine faster than necessary, resulting in too high an elemental iodine level, too rapid depletion of iodate, and ultim~tely no counterbalance of iodine loss through iodine regenera~ion The range o~ iodide concentration oP this invention is not characterized by sharp limits. The lower pre~erred -range limit of 0 05~ represents an amount which ordinarily must be present in order to provide a sufficient amount to react with the iodate. The upper preferred limit.provides both a large "reservoir" to be drawn ~rom, and the higher concentra-tion necessary whën large amounts o~ iodine have to be replen-ished, or with higher buf~ered pH, closer to pH 7, when a higher iodide concentration is desired to increase the rate o~ iodine formation The range of iodate ion, from any source, should start at about 0.005%, so that it can provide~ ultimately about 0 02~
.extra iodine in a ~ormulation. For most practical applications, an amount of 0.05 - 0.1~ can be used. Higher amounts can be used, dictated by e ~nomics.
The organic substance is an integral part of this invention in that all the uses contemplated concern maintaining the concentration o~ elemental iodine in an aqueous medium con-taining organic substances suc~h as a solvent, an iodine solu-bilizer~ an iodine complexing agent, etc., detergent~ or the like. Elemental iodine reacts more or less with all such organic substances which contain carbon, hydrogen, and oxygen ("C, N, nd 0"). Unless such C, H, 0 containing substance is .' ' .
.
~- I q~27~76 present, there is no need ~or this invention This inventio~
is applicable to essentially all previous aqueous "comple~e~
iodine" art typified b~ the subject matter in U S, Patents
2~9~1,777; 2,759,8G9; 3,028,299; ~,028,300 and many others Examples of solvents containing C, H, and O ordinarily used with iodine are ethanol, propanol~ isopropanol, propylene glycol, glycerine, polyethylene glycol. These are given by way o~ illustration, not limitation.
E~amples of surface active agents containing C, H, and O ordinarily used with iodine are ethoxylates of alkyl-phenols, of moderate length alcohols, of polyoxypropylene, anionic detergents that are sulfated, sulfonated, phosphated, carboxylated etc. Theseg too, are given by wa~ of illustration, not limitation.
Similarly, this invention can be practiced with iodine in combination with other C, H~ and O containing subst'ances such as cationic substances and amphoteric substances. The specific organic substance containing C, H, and O is of no importance to this invention. It makes no difference whether the iodine is strongly complexed, weakly complexed, or not complexed at all. Kather, the need for this invention will be most apparent for weakly complexed iodine compositions~ since these generally show greater iodine losses while standing on the shelf compared with strongly complexed iodine.
A series of iodine compositions were prepared with and without addition of iod~te. The samples were stored for ~; 2~;!07.~i !j , a time period up to one week, in glass bottles, at room tem-perature (20-25C) and at 50C for conventional accelerated storage to simulate extended storage at room temperature. As soon as a non-iodate old art composition (e.~, lA~ 2A, etc,) lost all its iodine in the 50C oven, the iodate containing ¦¦ counterpart (e.g. lB, 2B, etc.) was removed and analyzed, 1~ After the last o~ the "A" series samples failed, less than j one week from the start of the 50C storage, all the room ¦ temperature samples were analyzed and the results recorded.
!~ (See following page for chart.) !i The results indicate a dramatic improvement in iodine !i stabilit,y in the "B" series compared with the old art "A"
Il series as a direct result of adding iodate to the formula-¦¦ tions over the pH range of about 6 through 7, The ~A~l series ¦i lost noticeably more iodine than the "B" series even after ¦¦ onl,y one week at room temperature.
I The compositions of Example 1 contain glycerine, pro-I pylene glycol, polyethylene gl,ycol 400 (PEG 400), and citric acid as the C, H, 0 containing organic substances that tend to react with iodine, In this particular example, no sur-i face active substances have been included so as to show that the new teaching extends bevond applications to detergent-~¦ iodine complexation art, ~
We have found that the rate at which a give.n amount Il ~ iodide and iodate react at a particular h,Ydrogen ion con-jj centration is not the same in the presence o~ C, H~ and 0 11 ' i.
1, i 76~
~1 ~ 0 ~ o aO~ o o.~, ;Z Z O O O _ ~ CT' o -- ~ C o~ ~ -- o;~
-l z æ o o z; -~ ~ o~ o o o , a ~ U~ o 60~ `D ~ O O O
,. ,1 æ-~zooo~ .
¢¦ e O C3 ~ U~ o~ `D ~ o o o.
; ~ _ Z ~ o Z ~ V' O O O
. . ' ;' ~ 0~ o I ~ æ 0 0 0 _ ~ O~
1 Z e ~ O O Z ~ O, ~, O.O O
o I e ~ o o e ~ ~ " o o o o 1 ~ o~3 ~ ~ O O ~ ~
il' ' ~ ~; z o o o _l ~ cr o o. o . I
sl # = ~ ~ = O ~ o Oo O
u~ 2; Z O O ~ -~ cr cr O O O
,~ ~ o E E ~ E ~ ~ c .iz7t~g ' containing substances compared with the same concentratlons of iodide, iodate, and hydrogen ions in pure water, The situation becomes rather complicated in that when C, H, and O containing substances are present, these substances re-ac-t with the iodine already present in the composition.
When the iodine compositions contain organic.substances tha~ are more reactive, iodine losses can be best balanced by A) lowering the pH in the range pH 5 - 7, B) using more iodide, and C) using more iodate. I
These parameters can be varied one at a time, two at a time, I
or all three together. When the iodine compositions contain less ~C, H, O" organic substances, or organic substances that are only slightly reactive with iodine, then less io-dide can be used if desired, less iodate, and a higher pH, in the range 5 - 7. Within the range of pH 5 - 7, there is an optimum pH to most closely balance iodine loss through formation of iodine in situ from the iodide and iodate in the iodine compositions of this invention. This optimum is usually within the preferred range,.pH 5.5 6.5 The compositions of Example 1, or simîlar composi-tions containing more or less glycerine~ propylene glycol, PEG 400, or the like, are suitable for use in dipping cows' teats after milking as a mastitis preventative~ The iodine in the composition is less firmly complexed than in t~pical iodine teat dip formulations containing about ]~ iodine 0.4~ iodide, and about 10~ of a nonionic detergent. Less I;
~27~6 , complexed iodine will kill bacteria faster than more com-plexed iodine. More important, the total iodine content in ii the Example 1 composi-tions is less than 0,5~, compared with , about 1,5~ for conventional'l~ elemental iodine teat dips,, making the Example 1 compositions less of' a hazard with re- j i, spect to possibl,y inadvertentl~ contaminating milk with iodine, ' j , The compositions of Example 1 may be modified b,y ¦l the addition of thickeners and iodine complexing agents such li as ethoxylated detergents, PVP, quaternar~y amonium compounds, ,il amphoteric detergents, etc., to achieve an,Y desired level ,j of iodine complexing. Whatever the final composition, the desired elemental iodine level can be maintained through ad-! dition of iodate and maintenance of pH in the ran~e o~ 5 - 7, Example 2 ,, A series of iodine compositions were prepared, suit-` able for.hand washing to remove and kill transient bacteria, i~ with and without addition of iodate. The samples were stored I for -two weeks at ambient temperature (21-26C) and at 35C in ¦¦' 'glass containers to simulate extended product storage at ambi-il ent temperature, Iodine was determined before and after storage, ii In these compositions, it has been found that as li-ttle as 0,002 elemental iodine will surpass the performance of 50 ppm of ~I chlorine by the A,O,A,C, "Available Chlorine Germicidal Equi-¦l valent Concentration Test", It has been customary to use io-¦i dine compositions for hand washing that contain 0,75 to 1.0~
I
!
:- 1127~)7~i ., , ,'..',', , elemental iodine, obviously a gross excess over the amount needed for killing transient bacteria Iodine hand washing compositions containing about 0.1~ elemental iodine or less, will find greater consumer acceptance since there is less ~ello~tJ
color, less odor, less staining, etc For this purpose, an iodine-content anywhere from 0~1~ to 0.01~ elemental iodine is satisfactory. The most suitable compositions will center around 0.025~, which gives a dark, straw colored product-with an almost colorless lather.
.(See following page for chart.) Composition.2A is not considered as an example o~ this invention since there is no iodate present. Rather it repre-sents the prior art~ an example in which the iodine has dropped from 0.050~ to 0.002~ at ambient temperature (21 - 26C) after two weeks. Since there is no iodine present in the ~5C sample, this means that the efficacy of this composition can not be ~uaranteed past about one month. Composition 2B, with no iodide in the sample other than the small amount formed from iodine as it reacts with organic matter, is likewise not suit-able for sale. In-other experiments we have noted that at least about p.025~ by weight of iodide ion must be present in order to be able to keep iodine generated in a meaningful amount by means of iodate. Composition 2C is an example showing borderline utility, owing to a minimum level of iodate. There is only about o.oo8~ iodate ion in this composition~ which soon becomes too depleted to serve as a reserve for satisfactory continued iodine generation. Composition 2D is shown as an ,:
~ %~;PV7~
. , . - .
U~ o U~
I o o Ct ~ o ~ ~ o o o U~ ~ o o o Z :: o o o o :C~ o o ~o ~ o o '`- " ~
U~ .~; o~ o o ,,, ~ ,, o o o . U~ o ~ Y~ o ,~" o o oO ~ . . X -~ o C7 ~ ~ o o o _~ ~ o o o ~ ~
. ,.
~ ~ .
U~ ~ ~ o U'~ ~ ~
~, o o o ~ o o _. o o o o o o _ ~ ~ o o o u~
~ o ~ ~ o U~ ~ ~
C~ o o _, ~ o _, o o o ~ o o o _, S o o o Ct Ql ~ , O O O
U'~ o o ~1 ~ O~ O O O
.. U~ ' ' .
C~. O ~ ~ ~: o~ ~ ~
, U~, ~ o o o ~ O O ~' . ~ , , .
~l ~ ~ ~ ~ o~
X o ~ o IP~ Ct ' .
¢l o o ~ ~ o o o . u~ c~J C~ O ~ cr O' O , . ~ a ~ ~
~ V ~ ~
~ . u, a ~ ~ ~: x .. . 5~ ~ V ~ ~
~ t ~I~
. ~ ~ 8 ~ u ~ a d !
I ~
L~76 ex ple where either the io~ide or iodate concentrat~on should be lowered a little in order to avoid the slight iodine e~cess, Alternatively~ the pH could be raised to close to p~I 7,0.
Compositions 2E and 2F are typical examples of satisfactory compositions which although not exactly the same s~rength as originally made, are stable. Compositions 2G and 2H are a pair to show that pH 7.0 is borderline and pH 7.5 is useless, even though:the hydrogen ion concentration digference is very small.
Composition 2I, with no buffer added performs as well as its buffered counterpart, 2F~ However, this is only because the pH
was still 6.3 at both temperatures, without the buffering. In situations where there is the possibility of ~he pH being significantly disturbed, buffering is essential. Additional compositions, not shown here, using lactate, and phosphate buffer, gave the same results. Below pH 5, it is virtually impossible to control the generation of iodine from added iodate. In terms of the purpose of this invention, iodine is generated too rapidly to be of any use. At pH 5 and above, to pH 7, judicious choice of iodide and iodate can solve the stability problem.
Example 3 A series of iodine compositions were prepared, suit-a~le ~or teat dipping of dairy cows, as a mastitis preventative, with and without the addition og iodate. The samples were stored for two weeks in glass containers at 50C to simulate e~tended product storage at ambient temperature, and were analyzed for iodine at the end of this period.
~ ~12~ 6 Ingredient (See following page for chart ) The compositions o~ Example ~ which are not covexed by this invention are the compositions wi-th no iodate, namel~
3A, 3C, 3E and 3G. The f`irst composition, ~A, would be accep table as a product even with an iodine loss of 0.2~ over two weeks at 50C, roughly equivalent to a year at ambient tempera-ture, since it could be released at 1.1~ and it would thenfall to 0.9~, an acceptable loss. Composition 3C could probably not be sold as a teat dip, since the iodine loss over the accelerated test period was 0.2%~ or 40~ on a relative basis~
compared with the original value. Compositions E and G are unthinkable as products.
However, the same compositions with iodate levels of 0.05 to 0.20~, compositions ~B, 3D, ~F and 3H, are distinctly improved from an elemental iodine stability standpoint, and compositions such as ~F and 3H would offer special advantage as teat dips with very low danger of inadvertent milk contamination possibility.
Below pH 5, at pH 4.5 for example, it is not practic~
able to add iodate, since ~odine concentration in the teat dip formula has been found to actually increase on standing.
Every detergent or iodine c~rrier or ~mplexer that is acceptable as a component in an aqueous eIemental iodine composition, can also be used for the purpose of this invention, and the resultant composition can be shown to have improved iodine stability after addition of iodate and pH adjustment in the range pH 5-7~
0~6 .
~1 o o o ~ , o I , Cr~ o o o o o, :~ o o o U~ ~
I . ~ ~
VlU~ 0 aV O 4~ 0 ~ _~ ~ O
. ~ o o o :Z o :: o o o U~ 3 ~
~ oo ~
o ~ ~
o o o o o :Z o o o ~ o ~J
I . ~ .
l ~ ~ ~ o "~ 3 ¦ ~ ~ , ~ , . 8 . ~ ~
l cr~ o o ~ X O:~ O O O L; ~: o l V y !
~ ~ o~
~ O O O O O :1: O' O O ~ ~ ~ -" ~ ~ oo ~
U~ l ~ o U~ o ~ ~ , ~ o o O X 0~ ~ ~ ~ ~
n. G ~1 ' ~ O ~
,1~ u~ O ~ O 1~) C\ O c ~ ~o 6~
o' ~ o o' o :~ o ~ ~ 15 ~ .i V S
~ ~ ~ o~ ~ ¢i ~ . ~.
¢l ~ O, S~ O a) ~ ~ ~
Cl~ O -~ O Z O ~ O _~ O U~. ~.o tO
~; ~
. ~ ~a .'" ~ o .
~ Q P~
U~ 3 P. ~ * ~C .f O
a~ ~ ¢ o2 ~ C a: _ nJ O ~ x C ~1 ~J
q~ o ~ o )' I~ S~
oc ~ V ~2 ~ '` ~ ~ '~ ~'i ~ ' o~ , ~ ~ ~ o W '~ ~ ~ U~
w P~ 3 w l ~i !~
-17~
Because the nature and amounts of organic compounds containing carbon, hydrogen and oxygen and o~ other ad~uvantg can be so widely varied, lt is di~icult to de~ne the inven~ion in terms of amounts, or ranges o~ amounts of components. This presents no problem to those wishing to use this invention as for any particular iodine composition desired to be marketed the optimum levels o~ iodide ion and iodate ion concentrations and the optimum pH adjustment within the range pH 5-7 can be deter-mined by making a few comparisons of the type presented herein, particularly in Example 2. Although looking for iodine stability over an extended period of months or years, meaningful indica-tions of the long range, ambient temperature stability are obtainable by "accelerated aging" as for example storing for two weeks at 50C~ or at some other temperature and time con-sidered appropriate for the particular composition and its intended use.
It should also be-noted that it is not essential to the success~ul practicing o~ this invention that the iodine level remain the same throughout an extended period of storage, Rather, what is important is that any change in iodine concen-tration be held within the limits of variation permissible for the particular type product.
Thus germicidal iodine solutions considered to be within the scope of the present invention are those in which optimum selections of iodide and iodate ion concentrations and pH within the pH 5 to 7 range ~or a particular composition are such that the iodine level during extended storage will remain within the range of variation permissible for such composition Various changes and modifications in the germicidal iodine compositions herein disclosed may occur to ~hose skilled in the art, and to the extent that such change~ and modifica-tions are embraced by the appended claims, it ls to be under-stood that they constitute part of the present invention.
E~amples of surface active agents containing C, H, and O ordinarily used with iodine are ethoxylates of alkyl-phenols, of moderate length alcohols, of polyoxypropylene, anionic detergents that are sulfated, sulfonated, phosphated, carboxylated etc. Theseg too, are given by wa~ of illustration, not limitation.
Similarly, this invention can be practiced with iodine in combination with other C, H~ and O containing subst'ances such as cationic substances and amphoteric substances. The specific organic substance containing C, H, and O is of no importance to this invention. It makes no difference whether the iodine is strongly complexed, weakly complexed, or not complexed at all. Kather, the need for this invention will be most apparent for weakly complexed iodine compositions~ since these generally show greater iodine losses while standing on the shelf compared with strongly complexed iodine.
A series of iodine compositions were prepared with and without addition of iod~te. The samples were stored for ~; 2~;!07.~i !j , a time period up to one week, in glass bottles, at room tem-perature (20-25C) and at 50C for conventional accelerated storage to simulate extended storage at room temperature. As soon as a non-iodate old art composition (e.~, lA~ 2A, etc,) lost all its iodine in the 50C oven, the iodate containing ¦¦ counterpart (e.g. lB, 2B, etc.) was removed and analyzed, 1~ After the last o~ the "A" series samples failed, less than j one week from the start of the 50C storage, all the room ¦ temperature samples were analyzed and the results recorded.
!~ (See following page for chart.) !i The results indicate a dramatic improvement in iodine !i stabilit,y in the "B" series compared with the old art "A"
Il series as a direct result of adding iodate to the formula-¦¦ tions over the pH range of about 6 through 7, The ~A~l series ¦i lost noticeably more iodine than the "B" series even after ¦¦ onl,y one week at room temperature.
I The compositions of Example 1 contain glycerine, pro-I pylene glycol, polyethylene gl,ycol 400 (PEG 400), and citric acid as the C, H, 0 containing organic substances that tend to react with iodine, In this particular example, no sur-i face active substances have been included so as to show that the new teaching extends bevond applications to detergent-~¦ iodine complexation art, ~
We have found that the rate at which a give.n amount Il ~ iodide and iodate react at a particular h,Ydrogen ion con-jj centration is not the same in the presence o~ C, H~ and 0 11 ' i.
1, i 76~
~1 ~ 0 ~ o aO~ o o.~, ;Z Z O O O _ ~ CT' o -- ~ C o~ ~ -- o;~
-l z æ o o z; -~ ~ o~ o o o , a ~ U~ o 60~ `D ~ O O O
,. ,1 æ-~zooo~ .
¢¦ e O C3 ~ U~ o~ `D ~ o o o.
; ~ _ Z ~ o Z ~ V' O O O
. . ' ;' ~ 0~ o I ~ æ 0 0 0 _ ~ O~
1 Z e ~ O O Z ~ O, ~, O.O O
o I e ~ o o e ~ ~ " o o o o 1 ~ o~3 ~ ~ O O ~ ~
il' ' ~ ~; z o o o _l ~ cr o o. o . I
sl # = ~ ~ = O ~ o Oo O
u~ 2; Z O O ~ -~ cr cr O O O
,~ ~ o E E ~ E ~ ~ c .iz7t~g ' containing substances compared with the same concentratlons of iodide, iodate, and hydrogen ions in pure water, The situation becomes rather complicated in that when C, H, and O containing substances are present, these substances re-ac-t with the iodine already present in the composition.
When the iodine compositions contain organic.substances tha~ are more reactive, iodine losses can be best balanced by A) lowering the pH in the range pH 5 - 7, B) using more iodide, and C) using more iodate. I
These parameters can be varied one at a time, two at a time, I
or all three together. When the iodine compositions contain less ~C, H, O" organic substances, or organic substances that are only slightly reactive with iodine, then less io-dide can be used if desired, less iodate, and a higher pH, in the range 5 - 7. Within the range of pH 5 - 7, there is an optimum pH to most closely balance iodine loss through formation of iodine in situ from the iodide and iodate in the iodine compositions of this invention. This optimum is usually within the preferred range,.pH 5.5 6.5 The compositions of Example 1, or simîlar composi-tions containing more or less glycerine~ propylene glycol, PEG 400, or the like, are suitable for use in dipping cows' teats after milking as a mastitis preventative~ The iodine in the composition is less firmly complexed than in t~pical iodine teat dip formulations containing about ]~ iodine 0.4~ iodide, and about 10~ of a nonionic detergent. Less I;
~27~6 , complexed iodine will kill bacteria faster than more com-plexed iodine. More important, the total iodine content in ii the Example 1 composi-tions is less than 0,5~, compared with , about 1,5~ for conventional'l~ elemental iodine teat dips,, making the Example 1 compositions less of' a hazard with re- j i, spect to possibl,y inadvertentl~ contaminating milk with iodine, ' j , The compositions of Example 1 may be modified b,y ¦l the addition of thickeners and iodine complexing agents such li as ethoxylated detergents, PVP, quaternar~y amonium compounds, ,il amphoteric detergents, etc., to achieve an,Y desired level ,j of iodine complexing. Whatever the final composition, the desired elemental iodine level can be maintained through ad-! dition of iodate and maintenance of pH in the ran~e o~ 5 - 7, Example 2 ,, A series of iodine compositions were prepared, suit-` able for.hand washing to remove and kill transient bacteria, i~ with and without addition of iodate. The samples were stored I for -two weeks at ambient temperature (21-26C) and at 35C in ¦¦' 'glass containers to simulate extended product storage at ambi-il ent temperature, Iodine was determined before and after storage, ii In these compositions, it has been found that as li-ttle as 0,002 elemental iodine will surpass the performance of 50 ppm of ~I chlorine by the A,O,A,C, "Available Chlorine Germicidal Equi-¦l valent Concentration Test", It has been customary to use io-¦i dine compositions for hand washing that contain 0,75 to 1.0~
I
!
:- 1127~)7~i ., , ,'..',', , elemental iodine, obviously a gross excess over the amount needed for killing transient bacteria Iodine hand washing compositions containing about 0.1~ elemental iodine or less, will find greater consumer acceptance since there is less ~ello~tJ
color, less odor, less staining, etc For this purpose, an iodine-content anywhere from 0~1~ to 0.01~ elemental iodine is satisfactory. The most suitable compositions will center around 0.025~, which gives a dark, straw colored product-with an almost colorless lather.
.(See following page for chart.) Composition.2A is not considered as an example o~ this invention since there is no iodate present. Rather it repre-sents the prior art~ an example in which the iodine has dropped from 0.050~ to 0.002~ at ambient temperature (21 - 26C) after two weeks. Since there is no iodine present in the ~5C sample, this means that the efficacy of this composition can not be ~uaranteed past about one month. Composition 2B, with no iodide in the sample other than the small amount formed from iodine as it reacts with organic matter, is likewise not suit-able for sale. In-other experiments we have noted that at least about p.025~ by weight of iodide ion must be present in order to be able to keep iodine generated in a meaningful amount by means of iodate. Composition 2C is an example showing borderline utility, owing to a minimum level of iodate. There is only about o.oo8~ iodate ion in this composition~ which soon becomes too depleted to serve as a reserve for satisfactory continued iodine generation. Composition 2D is shown as an ,:
~ %~;PV7~
. , . - .
U~ o U~
I o o Ct ~ o ~ ~ o o o U~ ~ o o o Z :: o o o o :C~ o o ~o ~ o o '`- " ~
U~ .~; o~ o o ,,, ~ ,, o o o . U~ o ~ Y~ o ,~" o o oO ~ . . X -~ o C7 ~ ~ o o o _~ ~ o o o ~ ~
. ,.
~ ~ .
U~ ~ ~ o U'~ ~ ~
~, o o o ~ o o _. o o o o o o _ ~ ~ o o o u~
~ o ~ ~ o U~ ~ ~
C~ o o _, ~ o _, o o o ~ o o o _, S o o o Ct Ql ~ , O O O
U'~ o o ~1 ~ O~ O O O
.. U~ ' ' .
C~. O ~ ~ ~: o~ ~ ~
, U~, ~ o o o ~ O O ~' . ~ , , .
~l ~ ~ ~ ~ o~
X o ~ o IP~ Ct ' .
¢l o o ~ ~ o o o . u~ c~J C~ O ~ cr O' O , . ~ a ~ ~
~ V ~ ~
~ . u, a ~ ~ ~: x .. . 5~ ~ V ~ ~
~ t ~I~
. ~ ~ 8 ~ u ~ a d !
I ~
L~76 ex ple where either the io~ide or iodate concentrat~on should be lowered a little in order to avoid the slight iodine e~cess, Alternatively~ the pH could be raised to close to p~I 7,0.
Compositions 2E and 2F are typical examples of satisfactory compositions which although not exactly the same s~rength as originally made, are stable. Compositions 2G and 2H are a pair to show that pH 7.0 is borderline and pH 7.5 is useless, even though:the hydrogen ion concentration digference is very small.
Composition 2I, with no buffer added performs as well as its buffered counterpart, 2F~ However, this is only because the pH
was still 6.3 at both temperatures, without the buffering. In situations where there is the possibility of ~he pH being significantly disturbed, buffering is essential. Additional compositions, not shown here, using lactate, and phosphate buffer, gave the same results. Below pH 5, it is virtually impossible to control the generation of iodine from added iodate. In terms of the purpose of this invention, iodine is generated too rapidly to be of any use. At pH 5 and above, to pH 7, judicious choice of iodide and iodate can solve the stability problem.
Example 3 A series of iodine compositions were prepared, suit-a~le ~or teat dipping of dairy cows, as a mastitis preventative, with and without the addition og iodate. The samples were stored for two weeks in glass containers at 50C to simulate e~tended product storage at ambient temperature, and were analyzed for iodine at the end of this period.
~ ~12~ 6 Ingredient (See following page for chart ) The compositions o~ Example ~ which are not covexed by this invention are the compositions wi-th no iodate, namel~
3A, 3C, 3E and 3G. The f`irst composition, ~A, would be accep table as a product even with an iodine loss of 0.2~ over two weeks at 50C, roughly equivalent to a year at ambient tempera-ture, since it could be released at 1.1~ and it would thenfall to 0.9~, an acceptable loss. Composition 3C could probably not be sold as a teat dip, since the iodine loss over the accelerated test period was 0.2%~ or 40~ on a relative basis~
compared with the original value. Compositions E and G are unthinkable as products.
However, the same compositions with iodate levels of 0.05 to 0.20~, compositions ~B, 3D, ~F and 3H, are distinctly improved from an elemental iodine stability standpoint, and compositions such as ~F and 3H would offer special advantage as teat dips with very low danger of inadvertent milk contamination possibility.
Below pH 5, at pH 4.5 for example, it is not practic~
able to add iodate, since ~odine concentration in the teat dip formula has been found to actually increase on standing.
Every detergent or iodine c~rrier or ~mplexer that is acceptable as a component in an aqueous eIemental iodine composition, can also be used for the purpose of this invention, and the resultant composition can be shown to have improved iodine stability after addition of iodate and pH adjustment in the range pH 5-7~
0~6 .
~1 o o o ~ , o I , Cr~ o o o o o, :~ o o o U~ ~
I . ~ ~
VlU~ 0 aV O 4~ 0 ~ _~ ~ O
. ~ o o o :Z o :: o o o U~ 3 ~
~ oo ~
o ~ ~
o o o o o :Z o o o ~ o ~J
I . ~ .
l ~ ~ ~ o "~ 3 ¦ ~ ~ , ~ , . 8 . ~ ~
l cr~ o o ~ X O:~ O O O L; ~: o l V y !
~ ~ o~
~ O O O O O :1: O' O O ~ ~ ~ -" ~ ~ oo ~
U~ l ~ o U~ o ~ ~ , ~ o o O X 0~ ~ ~ ~ ~
n. G ~1 ' ~ O ~
,1~ u~ O ~ O 1~) C\ O c ~ ~o 6~
o' ~ o o' o :~ o ~ ~ 15 ~ .i V S
~ ~ ~ o~ ~ ¢i ~ . ~.
¢l ~ O, S~ O a) ~ ~ ~
Cl~ O -~ O Z O ~ O _~ O U~. ~.o tO
~; ~
. ~ ~a .'" ~ o .
~ Q P~
U~ 3 P. ~ * ~C .f O
a~ ~ ¢ o2 ~ C a: _ nJ O ~ x C ~1 ~J
q~ o ~ o )' I~ S~
oc ~ V ~2 ~ '` ~ ~ '~ ~'i ~ ' o~ , ~ ~ ~ o W '~ ~ ~ U~
w P~ 3 w l ~i !~
-17~
Because the nature and amounts of organic compounds containing carbon, hydrogen and oxygen and o~ other ad~uvantg can be so widely varied, lt is di~icult to de~ne the inven~ion in terms of amounts, or ranges o~ amounts of components. This presents no problem to those wishing to use this invention as for any particular iodine composition desired to be marketed the optimum levels o~ iodide ion and iodate ion concentrations and the optimum pH adjustment within the range pH 5-7 can be deter-mined by making a few comparisons of the type presented herein, particularly in Example 2. Although looking for iodine stability over an extended period of months or years, meaningful indica-tions of the long range, ambient temperature stability are obtainable by "accelerated aging" as for example storing for two weeks at 50C~ or at some other temperature and time con-sidered appropriate for the particular composition and its intended use.
It should also be-noted that it is not essential to the success~ul practicing o~ this invention that the iodine level remain the same throughout an extended period of storage, Rather, what is important is that any change in iodine concen-tration be held within the limits of variation permissible for the particular type product.
Thus germicidal iodine solutions considered to be within the scope of the present invention are those in which optimum selections of iodide and iodate ion concentrations and pH within the pH 5 to 7 range ~or a particular composition are such that the iodine level during extended storage will remain within the range of variation permissible for such composition Various changes and modifications in the germicidal iodine compositions herein disclosed may occur to ~hose skilled in the art, and to the extent that such change~ and modifica-tions are embraced by the appended claims, it ls to be under-stood that they constitute part of the present invention.
Claims (10)
PROPERT~ OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A germi.cidal iodine composition comprlsing an aqueous solution of elemental iodine in a ~ermicidally effective amount not exceeding about 1.0~ and a-t least one organic sub~
stance which slowly reacts with iodine selected from the yroup consisting of iodine complexing polymers, surface active agents, alcohols, polyols and water soluble solvents, said organic sub-stance constituting 1 to 50.~ by weight of said composition, wherein iodine loss during extended storage due to such reaction is controlled by providing in said composition balanced sources of iodide ion in the range of about 0.025% to 0.5% and iodate ion in the range of about Q.005~ to 0.2~ while maintaining a pH within the range of pH. 5-7.
stance which slowly reacts with iodine selected from the yroup consisting of iodine complexing polymers, surface active agents, alcohols, polyols and water soluble solvents, said organic sub-stance constituting 1 to 50.~ by weight of said composition, wherein iodine loss during extended storage due to such reaction is controlled by providing in said composition balanced sources of iodide ion in the range of about 0.025% to 0.5% and iodate ion in the range of about Q.005~ to 0.2~ while maintaining a pH within the range of pH. 5-7.
2. A germicidal iodine composition as defined in claim 1, wherein the pH is controlled within the range pH 5.5-6.5.
3. A germicidal iodine composition as defined in claim 1, wherQin control of pX is enhanced by including a buffering agent.
4. A germicidal iodine composition as defined in claim 1, wherein the amount of elemental iodine is within the range of 0.01 to 0.25~.
5. A germicidal iodine composition as defined in claim 1, wherein said organic substance comprises at least one adjuvant selected from the group consisting of surface active substances, foam stabilizers, complexing agents, thic~eners and solvents.
6. A germicidal iodine composition as defined in claim 5, wherein adjuvants are selected to provide a composition adapted for topical application to animal tissue.
7. A germicidal iodine composition as defined in claim 6, wherein adjuvants are selected to provide a composition adapted for use as a hand washing composition.
8. A germicidal iodine composition as defined in claim 6, wherein adjuvants are selected to provide a composition adapted for use as a bovine teat dip.
9. A germicidal iodine composition as defined in claim 1, wherein the iodide ion concentration is in the range of about 0.05% to 0.5%.
10. A germicidal composition as defined in claim 1, wherein the iodine concentration is about 0.01 to 0.1%, the io-dide ion concentration is about 0.05 to 0.5%, the iodate ion concentration is about 0.05 to 0.1%, and the pH is within the range of pH 5.5 to 6.5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77,787 | 1979-09-21 | ||
| US06/077,787 US4271149A (en) | 1979-09-21 | 1979-09-21 | Germicidal iodine compositions with enhanced iodine stability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127076A true CA1127076A (en) | 1982-07-06 |
Family
ID=22140054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA360,395A Expired CA1127076A (en) | 1979-09-21 | 1980-09-17 | Germicidal iodine compositions with enhanced iodine stability |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US4271149A (en) |
| JP (1) | JPS5699419A (en) |
| AR (1) | AR228578A1 (en) |
| AU (1) | AU532821B2 (en) |
| BE (1) | BE885300A (en) |
| BR (1) | BR8005961A (en) |
| CA (1) | CA1127076A (en) |
| CH (1) | CH645807A5 (en) |
| DE (1) | DE3034290A1 (en) |
| DK (1) | DK162962C (en) |
| ES (1) | ES495562A0 (en) |
| FR (1) | FR2465418A1 (en) |
| GB (1) | GB2060385B (en) |
| IE (1) | IE50792B1 (en) |
| IT (1) | IT1220974B (en) |
| MX (1) | MX6446E (en) |
| NL (1) | NL185754C (en) |
| NZ (1) | NZ194835A (en) |
| ZA (1) | ZA805544B (en) |
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| US2759869A (en) * | 1952-01-05 | 1956-08-21 | West Laboratories Inc | Germicidal iodine preparations |
| US2918400A (en) * | 1956-04-16 | 1959-12-22 | Chilean Nitrate Sales Corp | Sanitizing compositions |
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| JPS54105200A (en) * | 1978-01-27 | 1979-08-17 | Texaco Development Corp | Preparation of iodine compound |
-
1979
- 1979-09-21 US US06/077,787 patent/US4271149A/en not_active Expired - Lifetime
-
1980
- 1980-09-03 NZ NZ194835A patent/NZ194835A/en unknown
- 1980-09-04 AU AU62051/80A patent/AU532821B2/en not_active Expired
- 1980-09-08 ZA ZA00805544A patent/ZA805544B/en unknown
- 1980-09-11 DE DE19803034290 patent/DE3034290A1/en active Granted
- 1980-09-12 GB GB8029629A patent/GB2060385B/en not_active Expired
- 1980-09-17 IE IE1945/80A patent/IE50792B1/en not_active IP Right Cessation
- 1980-09-17 CH CH693980A patent/CH645807A5/en not_active IP Right Cessation
- 1980-09-17 CA CA360,395A patent/CA1127076A/en not_active Expired
- 1980-09-18 BR BR8005961A patent/BR8005961A/en not_active IP Right Cessation
- 1980-09-19 FR FR8020184A patent/FR2465418A1/en active Granted
- 1980-09-19 AR AR282595A patent/AR228578A1/en active
- 1980-09-19 MX MX809041U patent/MX6446E/en unknown
- 1980-09-19 ES ES495562A patent/ES495562A0/en active Granted
- 1980-09-19 NL NLAANVRAGE8005251,A patent/NL185754C/en not_active IP Right Cessation
- 1980-09-19 DK DK398080A patent/DK162962C/en not_active IP Right Cessation
- 1980-09-19 BE BE0/202155A patent/BE885300A/en not_active IP Right Cessation
- 1980-09-22 IT IT24820/80A patent/IT1220974B/en active
- 1980-09-22 JP JP13220880A patent/JPS5699419A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| ES8106757A1 (en) | 1981-09-01 |
| IT1220974B (en) | 1990-06-21 |
| BE885300A (en) | 1981-03-19 |
| DK162962C (en) | 1992-05-25 |
| CH645807A5 (en) | 1984-10-31 |
| ZA805544B (en) | 1981-09-30 |
| JPS632242B2 (en) | 1988-01-18 |
| ES495562A0 (en) | 1981-09-01 |
| FR2465418A1 (en) | 1981-03-27 |
| GB2060385A (en) | 1981-05-07 |
| NZ194835A (en) | 1983-11-18 |
| IE50792B1 (en) | 1986-07-23 |
| JPS5699419A (en) | 1981-08-10 |
| DK398080A (en) | 1981-03-22 |
| IE801945L (en) | 1981-03-21 |
| DE3034290C2 (en) | 1991-04-11 |
| US4271149B1 (en) | 1983-04-19 |
| NL8005251A (en) | 1981-03-24 |
| NL185754B (en) | 1990-02-16 |
| US4271149A (en) | 1981-06-02 |
| IT8024820A0 (en) | 1980-09-22 |
| GB2060385B (en) | 1983-06-29 |
| AU6205180A (en) | 1981-03-26 |
| NL185754C (en) | 1990-07-16 |
| DK162962B (en) | 1992-01-06 |
| MX6446E (en) | 1985-05-31 |
| AU532821B2 (en) | 1983-10-13 |
| AR228578A1 (en) | 1983-03-30 |
| DE3034290A1 (en) | 1981-04-02 |
| BR8005961A (en) | 1981-03-31 |
| FR2465418B1 (en) | 1984-10-26 |
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