US3663694A - Iodophor dairy sanitants - Google Patents

Abstract

AN IODOPHOR UDDER SANITISING AGENT FOR COWS CONTAINS AN ALKOXYLATED LANOLIN DERIVATIVE IN PLACE OF PART OR ALL OF THE CONVENTIONAL NON-IONIC SURFACTANT USED HERETOFORE, COMPLEXED WITH IODINE. IF ANOTHER NON-IONIC SURFACTANT IS PRESENT, IT MAY BE A SURFACTANT WITH RO WITHOUT TERMINAL HYDROXYL GROUPS.

Description

United States Patent 3,663,694 IODOPHOR DAIRY SANITANTS Sean Geoffrey Hall, Belfast, Northern Ireland, assignor to Kilco Chemicals Limited, Belfast, Northern Ireland No Drawing. Continuation-impart of application Ser. No. 656,342, July 27, 1967. This application Dec. 19, 1968, Ser. No. 785,331 Claims priority, application Great Britain, July 27, 1966, 33,712/66 Int. Cl. A611 13/00 U.S. Cl. 424-238 Claims ABSTRACT OF THE DISCLOSURE An iodophor udder sanitising agent for cows contains an alkoxylated lanolin derivative in place of part or all of the conventional non-ionic surfactant used heretofore, complexed with iodine. If another non-ionic surfactant is present, it may be a surfactant with or without terminal hydroxyl groups.

This application is a continuation-in-part of my earlier application 656,342 filed July 27, 1967 and now abandoned.

This invention relates to iodophor dairy sanitising agents and particularly iodophor udder sanitising agents. An iodophor is a complex of iodine with a non-ionic surface-active agent which makes iodine available for sanitising purposes when in contact with water.

Iodophor preparations in which a part or all of the elementary iodine content is complexed with non-ionic surfactants are commonly used as sanitising agents in the diary industry. They are used particularly to dip cows udders, in, after milking, to inhibit mastitis.

Continual use of iodophor disinfectants has resulted in a widespread incidence of teat cracking. Cracks or fissures in the dermal tissue of the cows teat act as residence points for bacterial colonies and it is diflicult to penetrate these points with any type of water-borne disinfectant. It is assumed that the dermatological changes resulting in cracking are due to dennding of the skins natural protective fats by a process of emulsification.

Whilst iodophor preparations have high bactericidal activity, many of them suifer from the disadvantage that high percentages of ethoxylated surfactants are required for full solubilization of their elementary iodine content; it is recognised that only about 20% of the added iodine is chemically combined with the surfactant, the remainder being titratible analytically with standard sodium thiosulphate solutions. A high content of non-ionic surfactant in a conventional iodophor preparation however has strong degreasing properties on the skin. Free elementary iodine also is harsh on the skin.

The cheapest and most widely available non-ionic surfactants are alkoxylated compounds having a free terminal hydroxyl group on the alkoxy chain. However it has already been stated in literature that these surfactants are unsatisfactory for iodophor formulations due to shelf life instability which is presumed to be caused by interaction between iodine and the terminal hydroxyl groups.

One previous proposal for overcoming the solubility factor was described in British patent specification No. 825,676 which suggested employing an alkali halide, e.g. sodium iodide, in the formulation. It is assumed that this results in production of the I -ion.

It is an object of the present invention to provide an Patented May 16, 1972 ice iodophor dairy sanitising agent which does not cause teat cracking, which can contain relatively high percentages of iodine and surfactant, and which has good shelf stability even when a non-ionic surfactant having nonaromatic terminal OH groups is used.

The present invention provides an iodophor udder sanitising agent in which the iodophor consists at least in part of a complex of iodine with a water-soluble alkoxylated lanolin derivative. By alkoxylated lanolin derivative is meant the product formed by the condensation of an al-kylene oxide and lanolin.

Preferably the alkoxylated lanolin derivative is ethoxylated lanolin which may also be described as the polyethylene oxide derivative of lanolin. However, the use of the polypropylene oxide derivative is also envisaged, and it is a feature of this invention that any water-soluble polyalkylene oxide derivative of lanolin may be used, particularly those having alkyl groups containing 2- 8 carbon atoms.

The degree of condensation between the lanolin and alkylene oxide is not critical, but will generally be within the range of 6 to 100. The preferred average degree of condensation is about moles for ethylene oxide and about to for propylene oxide.

The invention also provides a method of preparing an iodophor udder sanitising agent which comprises forming a complex of iodine with a water soluble alkoxylated lanolin derivative.

A non-ionic surfactant other than the alkoxylated lanolin derivatives may also be present, complexed with iodine in the iodophor. In this case, the alkoxylated lanolin derivative should be mixed with the other non-ionic surfactant before iodine is added. Poo-r stability results if the lanolin derivative is added after iodine has combined with the other non-ionic surfactant.

The invention further provides a method of disinfecting cows udders which comprises treating the udders with an idophor udder sanitising agent as defined above, usually after dilution of the sanitising agent with water.

It is believed that the alkoxylated lanolin derivative is absorbed into the udder dermal tissues, producing an emollient action which succeeds in suppressing teat cracking. The lanolin derivative is substansive to the skin of animals, and therefore can take the place of any fact which may be removed by the non-ionic surfactant (if present).

The sanitising agent may also contain small percentages of an organic acid such as citric acid, propionic acid, tartaric acid or maleic acid. The organic acid keeps the pH value on the slightly acid side which is normal for teat tissue where the natural acidity is due to amine acids produced by normal protein degradation.

The alkoxylated lanolin derivative may make up from 15 to by weight of the total surfactant. When another non-ionic surfactant is present, it may be a surfactant with or without terminal OH groups. Preferred surfactants having terminal OH groups are ethoxylated nonyl phenol and ethoxylated octyl phenol (or nonyl phenol polyethylene glycol ether and octyl phenol polyethylene glycol ether).

Preferred ethoxylated octyl or nonyl phenols are those which have been produced by the condensation of at least nine molecules of ethylene oxide with the phenol in question. It is possible to use condensation products containing less than nine moles of the ethylene oxide, inasmuch as they do absorb iodine, but these products tend to be more difficult to disperse in water.

A preferred upper moles condensation ratio for these ethoxylated phenols lies at about 14 molecules of ethylene oxide per mole of phenol.

An example of a surfactant having no terminal OH groups is that sold under the trade name Texofor ISU by Glovers Chemicals.

Importance is attached in this invention to the difference between lanolin itself and an alkoxylated lanolin. Lanolln is a water-insoluble animal secretion and a complex mixture of fatty compounds and sterols. Alkoxylated lanolin is no less complex (after a condensation reaction with a reactive substance such as an alkylene oxide even more complexity of structure might be expected) but is water-soluble. The nature of the complex between the iodine and the alkoxylated lanolin is even more difficult to elucidate. Iodine is present in at least two forms in the iodophor according to the invention, and to this extent the teaching of, for example, US. Pat. 3,380,923 which makes the assumption that a relative uniform complex, or simple chemical bond, as present is not relevant to the more complex formulation of the present invention.

Although the individual components of the present formulation primarily alkoxylated lanolin and the various surfactants together with iodine were individually known previously, the new combination of these components was not known and its advantages were not to be predicted any more than the complexity of the mixture can be fully elucidated. These advantages are:

(i) the new composition is more bland to the skin than would have been expected from a consideration of the effect of a known iodine/surfactant composition merely soothed with the emollient action of any compatible amount of lanolin.

(ii) the formulation has an unexpected good shelf life.

(iii) not only the effect of the included detergent but also the dermatological effect of the iodine on the animal skin can be mitigated.

These advantages will be explained in more detail below.

Prior art iodophors based on octyl and nonyl phenols have poor storage stability. Their terminal non-aromatic OH groups are eventually reactive with the elementary iodine of the iodophor with the result that thiosulphate titrations of the product over a storage period reveal that the active sanitizing iodine concentration falls ofi? and can produce iodated products which in certain cases can actually be skin irritants. In this work it has been shown that iodine does react with non-ionic surfactants such as ethoxylated nonyl and octyl phenols and that iodine losses, in the titratable sense, can be as high as 7% if the product is stored over three months under normal daylight conditions. Iodophors containing octyl and nonyl phenols, or any other non-ionic surfactant having a terminal OH group in the alkoxylated chain seem to behave simliarly. It has been found, however, that mixtures of such nonionic surfactants together with alkoxylated lanolin have good storage life; e.g. titrations using thiosulphate carried out before and after 124 days storage at room temperature and in the presence of daylight, have only differed by as little as 0.1 mls. N/ 10 sodium thiosulphate and this is well within the limit of error in any experimental titration. Whilst it is no part of this specification to elucidate the physicochemical reactions leading to this stable state it is suggested that the stability of our product as herein described could be attributed to some form of hydrogen bonding between the alkoxylated lanolin and the non-ionic surfactant used.

Iodophor sanitising agents normally can have iodine concentrations within the range 0.25 to 2.5%. In the product of the invention the presence of the lanolin derivative diminishes the dermatological harshness of the elemental iodine and therefore high concentrations of iodine in the range 1.5 to 2.5 can be used. In tests carried out at a concentration of 2% iodine it is found there is no toxicity to the skin.

Most reported iodophors have non-ionic surfactant contents ranging from 5-25%. If iodine-surfactant interaction occurs in any of these products the rate of reaction will be dependent on the concentration of the surfactant and consequently for shelf stability the manufacturer will endeavour to keep the surfactant concentration as low as possible consistent with solubilisation of the iodine. Such products may be sanitising but their detergency will be low. In this particular specification since the problem of shelf stability has been overcome it is possible to produce sanitising detergents with detergent activities as high as 2025%.

An organic solvent such as an alcohol may be present to control viscosity and endow the product with antifreeze characteristics in countries where low temperatures prevail.

Unmodified anhydrous lanolin may be included in the formulation to further improve the dermatological properties of the formulation. Thus a combination of ethoxylated lanoline and anhydrous unmodified lanolin may be used.

The invention is illustrated in the following examples of iodophor udder sanitising agents.

EXAMPLE 1 Ethoxylated lanolin (degree of condensation about 75) 15 lbs.

Iodine-2 lbs.

Citric acid3 lbs.

Isopropanolil0 pints.

Water to give a total of 10 gallons.

EXAMPLE 2 Ethoxylated octyl phenol (about 12 moles ethylene oxide per mole of condensate10 lbs.

Iodine-2 lbs.

Citric acid3 lbs.

Ethoxylated lanolin (degree of condensation about 75) 5 lbs. I

Isopropanol--1O pints.

Water to give a total of 10 gallons.

Ethoxylated nonyl phenol may be used in the formulations of Examples 2 and 3 with similar results.

EXAMPLE 3 A formulation containing 20% by weight of anhydrous lanolin and by weight of:

Ethoxylated lanolin (degree of condensation about 75 15 lbs.

Iodine-2 lbs.

Citric acid3 lbs.

Isopropanol 10 pints.

EXAMPLE 4 Ethoxylated lanolin (degree of condensation about 75 10 lbs.

A formulation containing 20% by weight anhydrous lanolin and 80% by weight of ethoxylated lanolin- 5 lbs.

Iodine2 lbs.

Citric acid3 lbs.

Isopropanol--l0 pints.

In Example 4 the lanolin ethoxylated lanolin formulation may be replaced by a formulation containing 25% anhydrous lanolin and 75% of an alkoxylated fatty alcohol.

The effectiveness of the formulation of the invention will be illustrated by the following table, in which the effect of the iodophor of the invention (Example 2) is compared with that of a standard known iodophor and a control in which no iodophor is applied to the udder.

Iodophor of Standard the invention iodophor Control 1. Total number of animals treated 212 197 153 N um- Per- Num- Per- Num- Perber cent her cent ber cent 2. Animals showing teat-cracks at beginning of trial 126 59 106 54. 37 24 3. Animals showing no teat-cracks at beginning of trial 86 41 91 46 116 76 4. Animals showing teat-cracks at end of trial 47 132 67 31 20 5. Animals showing no teat-cracks at end of trial 113 53 65 33 122 80 NOTE.1. Out of 99 animals in the invention" group with teatcracks at the end of the trial, 38 of these animals had only very slight teat cracking and the cracking disappeared after days dipping at the end of the trial; 2. Out of 126 animals in the invention group which had teat cracks at the beginning of the trial, 69% of these animals had been previously dipped in a standard iodophor for a period of at least 10 weeks; 3. In the standard iodophor group 28% of the animals without cracks at the beginning of the trial developed cracks during the trial Le. 26 out of 91; 4. Out of 106 animals in the standard iodophor group, with teat-cracks at the beginning of the trial, 14% of these animals had been previously dipped 1n a standard iodophor for at least 7 weeks; 5. In these tests the bactericidal activity of the odophor of the invention was as good as that of the standard iodophor.

-I claim:

1. A method of disinfecting cows udders which comprises contacting the udders with an udder-santising amount of an iodophor comprising a complex of iodine with a surfactant, said surfactant including from to 100% of a water soluble ethoxylated lanolin derivative (formed by a condensation reaction between 6 to 100 molar parts of ethylene oxide with each part of lanolin, whereby the iodophor further acts to reduce teat cracking.

2. A method according to claim 1 wherein the iodophor also comprises a complex of iodine with a non-ionic surfactant comprising an ethoxylated octyl phenol formed by reaction of from 9 to about 14 moles of ethylene oxide per mole of phenol.

3. A method according to claim 2 wherein said nonlonic surfactant has in its molecule a chain-terminating hydroxyl group.

4. A method according to claim 1 wherein the sanitis- 1ng agent has a total iodine content of 1.5 to 2.5% by weight.

5. A method according to claim 1 wherein the sanitising agent further contains unmodified lanolin.

References Cited UNITED STATES PATENTS 4/1962 Winicov 424-341 4/1968 Beach 424-325 OTHER REFERENCES Terry et al., Proc. of the Che-m. Specialties Manuf. Assoc., December 1951, pp. 69-73.

McCutcheon, Detergents and Emulsifiers, 1966, p. 42.

Sagatin, Cosmetics-Science and Technology, 1957, Interscience Pub., p. 150.

STANLEY J. FRIEDMAN, Primary Examiner V. D. TUR'NER, Assistant Examiner U.S. C1. X.R.