DE2553956A1 - IODINE AND MIXTURES OF MICROBICIDALS CONTAINING AT LEAST ONE TERTIAER AMINOXIDE - Google Patents

Description

Saddle Brook, New Jersey, V.St.A.

"Containing iodine and at least one tertiary amine oxide microbicidal mixtures "

Priority: November 29, 1974, Great Britain, No. 51 844/74 August 28, 1975, Great Britain, No. 35 552/75

The effectiveness of iodine against microorganisms is known and has been exploited; see for example Arch. Biochem. Vol. 6, FB (1945), p. 261. Washing and cleaning agents, the solutions of free iodine in certain nonionic surfactants contain, are described in GB-PS 703 091, while in GB-PS 825 676 and 950 954 germicidal complexes of iodine with (a) quaternary ammonium compounds and (b) phenol-ethylene oxide condensates are described. Iodine-containing surfactants as acidic Solutions are described in GB-PS 962 955; Citric acid is used as the acid. In GB-PS 1 004 282 stability problems of mixtures of iodine and surfactants and described preparations containing iodine and iodide ions. From the GB-PS 1,066,437 shows the suitability of quaternary ammonium compounds for stabilizing iodine-containing agents. There will

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the use of a special class of non-ionic surfactants described as a carrier component. Mixtures of iodine and surfactants are described in a number of other publications, for example in GB-PS 1,167,743, 1,293,407 and 1,311,952, mixtures of iodine and amines are described in GB-PS 1,186,177 and 1 316 571.

The object of the invention is to find microbicidal mixtures containing iodine to create in which the presence of a surfactant or a quaternary ammonium compound is not essential which have good bactericidal, fungicidal and virucidal properties and generally good protection against the Cause infestation by harmful microorganisms.

The solution to the problem is based on the surprising finding that Mixtures containing iodine and at least one tertiary amine oxide have the above properties.

The invention thus relates to that characterized in the claims Object.

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The amine oxides used according to the invention preferably have the general formula I.

-N> 0 (I)

* 3

in which the radicals R 1, R ₂ and R _{3 are} identical or different and each represent an optionally substituted, unbranched or branched alkyl or alkoxy radical, an aromatic or heterocyclic radical.

As the above definition of the radicals R ₁ , R 2 and R_ shows, there is a very wide range of possible variations of these radicals in the amine oxides which can be used according to the invention can be substituted, provided the substituents do not impair the effectiveness of the amine oxide structure

-N-

impaired by complex formation with the iodine.

In a further preferred embodiment of the invention, at least one of the radicals R 1, R ₂ or R _{3 is in the aminoscides of the general formula I which can be used according to the invention}

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Tenneco Chemicals Inc., V. St .A. ^] "- " * ο cc η η ir Ω

uZ: L525 ·> ^ ". ^; · ^; 25539bb

- ΐ [NaohqereiohtI represents an optionally substituted pyridine or quinoline radical. In a further preferred embodiment of the invention, the amine oxide has the general formula II

R N> 0 (II)

CH ₃

in which the radical R is an optionally substituted unbranched or branched alkyl or alkoxy radical, in particular

mixture

a C, ~ -, C, "-, C ,, - C ₁₀ - substituted ethoxy radical or a / ± Z J.4 JLb - 'XcS

this means residues. A particularly preferred tertiary amine oxide is bis (2-hydroxyethyl) decylamine oxide.

Particularly preferred are those according to the invention, iodine and at least a tertiary amine oxide-containing mixtures dissolved in a liquid medium. Generally this consists of liquid Medium composed of water, a monohydric or polyhydric alcohol or mixtures of at least two of the above components. Preferably if the liquid medium in the mixtures according to the invention consists of glycerine or a mixture of glycerine and water. Another preferred liquid medium is water, wherein the mixtures according to the invention form an aqueous iodine-amine oxide solution.

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- s-

Furthermore, the mixtures according to the invention are preferably in acidic solution. They preferably contain the acid in such an amount that a 1 percent aqueous solution of the mixture a pH of at most 6, preferably a pH of 1 to 4.

The mixtures according to the invention preferably contain at least one of the acids mentioned below: hydrochloric acid, sulfuric acid, Phosphoric acid, sulfamic acid, hydroxyacetic acid and / or citric acid. In general, however, all water-soluble acids can be used.

Furthermore, the mixtures according to the invention preferably contain at least one nonionic, anionic or cationic surfactant or a mixture of at least two components. In general, all surfactants or mixtures thereof can be used, where mutual compatibility in the mixture is known. Therefore, an embodiment of the invention includes Mixture a mixture or a solution of at least one cationic and at least one nonionic surfactant, while another embodiment at least one nonionic and contains at least one anionic surfactant.

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Particularly preferred surfactants which can be used according to the invention are generally those obtained by reacting organic compounds containing active hydrogen atoms with a Alkylene oxide have been produced.

A specific example of a non-ionic which is preferably used Surfactant has the formula *

A specific example of a preferred anion-active one Surfactant has the formula:

₁ 2 ^H 25 ° - (CH ₂ GH ₂ O) 5-S

These two special surfactants are examples of the above-mentioned reaction products with an alkylene oxide.

The quaternary ammonium compound is particularly preferred as the cationic surfactant the formula:

CH ₅

Q θ CH ₂₉ H CHBr

CH ₅

The mixtures according to the invention preferably also contain at least a water soluble iodide such as potassium iodide. It has been found experimentally that the oxidizing Properties of the amine oxides used advantageously influenced

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j FOLLOWED j

■ _ ₇ _ * ZFEkJWo

as the amount of iodine available increases / however, the stability of the product is not impaired.

A particularly preferred mixture of the invention for combating harmful microorganisms is the product that by dissolving 3 parts by weight of iodine in 17 parts of a nonionic surfactant of the formula

Mixing the resulting solution with 5 parts by weight of a 30 to 45 percent aqueous solution of bis (2-hydroxyethyl) decylamine oxide and then acidifying the mixture by adding a solution of 13 parts by weight of sulfuric acid and 8 parts by weight of phosphoric acid in 66 parts by weight of water.

Another preferred mixture of the invention consists of a product obtained by dissolving 3.4 parts by weight of iodine in 19.6 parts by weight of a 25 percent aqueous solution of a tertiary amine oxide of the general formula II in which the

substituted, _g - ^c ]

represents, mixing the resulting solution with 19.4 parts by weight

R radical predominantly a C ₁ -, C ₁₄ -, C, _g -, ^c ] _8 'ethoxy radical

of a nonionic surfactant of the formula

H ₂₁ O - (CH ₂ CH ₂ O) ₉ - H

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and then acidifying the mixture by adding a solution of 13.3 parts by weight of sulfuric acid, 8.1 parts by weight of phosphoric acid in 36.2 parts by weight of water has been. By adding 0.4 parts by weight of potassium iodide to 100 parts by weight of this mixture, a Product with a higher content of available iodine.

The invention further relates to a method for producing the mixtures according to the invention, which is characterized in that that iodine is dissolved in a tertiary amine oxide.

In a preferred embodiment of the invention In the process, the iodine is first dissolved in a surfactant. The resulting solution is then mixed with a solution of the tertiary amine oxide and mixed with the solution of iodine in the surfactant. The resulting product is then acidified in such a way that a 1 percent aqueous solution of the acidified product has a pH of 6 or less.

It was found experimentally that mixtures according to the invention with particularly good bactericidal effectiveness by reaction from 0.5 to 20 parts by weight of iodine with 5 to 50 parts by weight of one, preferably by reacting an active one

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Organic compound containing hydrogen atom with an alkylene oxide, for example with ethylene oxide, propylene oxide or with their mixtures, prepared surfactant and adding 1 to 30 parts by weight of the tertiary to the resulting solution Amine oxide can be obtained as a stabilizer. The resulting product is then preferably acidified in such a way that that a 1 percent aqueous solution of the acidified product has a pH value of at most 4.

In a further preferred embodiment of the invention In the process, the iodine is first converted into the tertiary amine oxide dissolved and the resulting iodine-amine oxide solution then with a cationic, nonionic and / or anion-active surfactant, a mixture of at least one cation-active and at least one non-ionic surfactant or a mixture of at least one nonionic and at least one anionic surfactant and that the resulting product is then acidified in such a way that a 1 percent aqueous solution of the acidified product has a has a pH value of 6 or less. It was also found that mixtures according to the invention with particularly good bactericidal effectiveness and other desirable properties

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by reacting 0.5 Ms 20 parts by weight of iodine with 1 to 50 parts by weight of the tertiary amine oxide can be produced v / earth, after which the resulting solution subsequently with 1 to 30 parts by weight of a cationic, nonionic or anionic surfactant or with a mixture of cationic, nonionic or anionic surfactants or with them

Solution is added. Here, too, the resulting product is then acidified in such a way that it is 1 percent aqueous Solution of the acidified product has a pH of at most 6, preferably at most 4.

The examples illustrate the invention.

Example '1 17 parts by weight of a nonionic surfactant of the formula:

C ₁₀ H ₂₁ O - (CH ₂ CH ₂ O) ₉ -H

which has previously been heated to more than 4O ⁰ C, are mixed with 3 parts by weight of iodine. The resulting mixture is stirred until it is completely dissolved. The resulting solution is mixed with 5 parts by weight of a 30 to 45 percent solution of bis (2-hydroxyethyl) decylamine oxide in water and stirred. The resulting product is then mixed with a solution of 13 parts by weight of sulfuric acid and 8 parts by weight of phosphoric acid in 66 parts by weight of water and stirred. The resulting iodine-containing agent contains iodine,

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- li -

a tertiary amine oxide and a nonionic surfactant as a solution in the mineral acids.

Test methodology and results

See Section 3 (i) of the "Exemplary Note of the Approval of Disinfectants" for testing generally applicable disinfectants for the purpose of the Deseases of Animals Act 1950, "Department of Agriculture, Fisheries, and Food, Division Agriculture and Fisheries for Scotland published method showed the composition prepared according to Example 1 as aqueous solution at a dilution of 1: 180 growth inhibition. Details of the method used are given below:

When added to a yeast-microorganism mixture, the effective concentration of the disinfectant causes a germ count

Reduction of at least 10. The effective concentration is determined as follows:

The test is performed using a 24 hour old culture of Salmonella choleraesuis (N.C.T.C. No. 10653, N.C.I.B. # 10383) in an OXOID # 2 broth at 37+. 1 C carried out showing at least 10 viable germs per ml contains. Stock cultures of the test organisms are either in the form of freeze-dried ampoules or in blood agar tubes kept and in accordance with B.S.S. 808 1938 her-

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posed. The working culture is kept at a temperature of 37 + 1 ⁰ C until it is added to the yeast suspension.

A yeast suspension (5% dry substance) is prepared according to BSS 808 1938 and cooled to 4 + 0.5 ⁰ C. The disinfectant is mixed with sterile water with a hardness of 342 ppm (V / HO recipe) and brought to a temperature of

4 + O, 5 ° C cooled.

96 ml of the cold yeast suspension are mixed and dispersed with 4 ml of working culture and stored in 2.5 ml portions in a suitable number of test tubes of size 15-150 ml with metal caps. Each of the reagent tubes is then also at 4+. ü, 5 ° € with 2.5 al disinfectant in a suitable dilution «The resulting mixture is then immediately placed in a fresh, previously cooled test tube. The reagent tubes are then stored for 30 minutes at 4 ± 0.5 ^° C., shaking at intervals of 10 minutes. After 30 minutes, 0.1 ml of the mixture is added to 10 μl of nutrient broth (OXOID No. 2)

5 % horse serum content transferred. Each 1 ml of this dilution (1; 100) is then five nutrient broths each with a content of 9 ml OXOID Hr. 2 is added, after which it is incubated for 48 hours at 37 + 1 ° C.

Growth in at least two of the five nutrient media means growth retardation. Growth in more than three of the five nutrient media means no growth-inhibiting effect.

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According to the test procedure of disinfectant against tubercle bacilli according to method .3 (ix) of the above-mentioned "Exemplary Note" shows the agent produced according to Example 1 "Growth inhibition at a dilution of 1:50 with water. The following are more detailed information on the carried out Method:

The effective concentration of the disinfectant, when added to a yeast-microorganism mixture, causes a

Titer reduction of at least 10. Finding the effective concentration takes place as follows:

The test is carried out according to the test procedure for general-purpose disinfectants described above, but a 7-day-old culture of Mycobacterium fortuitum (NCTC No. 8573, NCIB No. 10384) is used as the test microorganism, and OXOID No. with a 0 is used as the culture medium .05 percent addition of TWEEN 80 is used. The contact time of the yeast-microorganism-disinfectant mixture is 60 minutes at 4 + 0.5 ^° C. and the incubation period is 7 days.

Example 2

19.6 parts by weight of EMPIGEN OY (registered trademark) are mixed with 3.4 parts by weight of iodine. EMPIGEN OY ® is a commercially available product is a 25 percent aqueous one Solution of an amine oxide of the general formula

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,, SUFFICIENTLY

V '(ID

R - H -> 0. ■ · ι

CH, 5

in which the radical R is mainly a C _1P ~ »C ₁ λ-, ^ iß ~ ^c io" substituted ^ Z y- ** ^lo

/ äthoxyrest represented / The EI-IPIGEN OY ^ was previously on

heated at most 40 ^{0 C.} The resulting mixture is then mixed with 19> 4 parts by weight of a nonionic surfactant. of the formula C ₁ ^ ₂₁ O- (OC ₂ H ^) ₉ -H added and stirred. A solution of 13.3 parts by weight of sulfuric acid and 8.1 parts by weight of phosphoric acid in 36) 2 parts by weight of barrels is then added to the resulting mixture and stirred. The resulting iodine-containing agent is of the general type described in Example 1 above.

B e i s ρ i e 1 3

100 parts by weight of the agent prepared according to Example 2 are mixed with 0.4 parts by weight of calcium iodide and stirred. The determination of the available iodine content (hereinafter referred to as "free iodine") in the products from Example 2 and 3 is carried out by titration with a standardized sodium thiosulfate solution. The following results are obtained:

Example 2 Example 3 Free iodine, weight percent 2.99 3 _f 20

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! In accordance with the test method described above for general purpose disinfectant according to the item 3 (i) from the 'Explanatory Notes of the Approval of Disinfectants for-the purpose of the Diseases of Animals Act, 195o ⁿ the above means show growth inhibition in the following dilutions:

Example 2: 1 part of medium to 180 parts of water Example 3: 1 part of medium to 200 parts of water.

According to the test procedure for anti-tuberculosis drugs according to Method 3 (ü) described above of the same "Explanatory Note "the above agents show growth inhibition at the following dilutions:

Example 2: 1 part of medium to 90 parts of water Example 3: 1 part of medium to 100 parts of water.

According to the Disinfectant Test Procedure for Foot and Mouth Disease Use by Method 3 of the above The "Explanatory Notes" given has that described in Example 3 Medium when the medium is diluted 1: 300 in water, it will inhibit growth. More details follow below Details of the method used:

The following test was carried out by the Animal Virus Research Institute carried out:

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The pH values of the disinfectant in hard water according to the WH0. Recipe, Eagle's Medium (10 %, cf. Macpherson, IA & Stoker, MGF (1962). Virology, 16, 147. Sellers, RF (1968). Vet . Rec. 83, 504), as well as bovine serum ( containing 0%, 10 % and 50% SO, are measured, and the concentration of the

will
Disinfectant / determined in which the presence of 50 % bovine serum would result in a logarithmic titer reduction of 4 in the virus titer (Seilers, 1968). The test is carried out by mixing the disinfectant in hard water (WH0.-recipe) in the concentration determined above with a content of 10 ^ bovine serum with foot-and-mouth disease viruses. The resulting mixture is ^{kept at 4 °} C. for 30 minutes, after which further dilutions are made in order to determine the titer of remaining viruses. The test result shows a decrease in the virus titer by

4th
at least 10.

According to the Avian Influenza Disinfectant Test Procedure (Newcastle Disease) 'according to Section 3 (iv) of the "Exemplary Note" described above shows that according to Example 3 Prepared means at a dilution of the means to water of 1: 150 growth inhibition. More details on the carried out method:

The following test for effectiveness against avian influenza was carried out in the "Central Veterinary Laboratory" in Weybridge and corresponds to the test described above for general purpose disinfectants, however

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avian influenza viruses from the Herts 33 strain as test microorganisms used.

The resultant test mixture was held for 30 minutes at 4 + _ 0.5 ° C and then is diluted by introduction into 5prozentiges inactivated horse serum. Further dilutions are made for virus titration. The disinfectant to be examined results in a reduction in the virus titer of at least 10.

In the following examples 4 with 7, that in example 2 tertiary amine oxide described used in the form of a 25 percent aqueous solution. The values for free iodine will be obtained according to Example 2 and 3.

The iodine values of the invention contain in Example 4, an anionic surfactant _r in Example 5, a cation-active Tenrsid, namely the ahqeqebene there quaternary ammonium compound, in Example 6, both a nichtiönogenes and a cation-active Tensiö and both an anionic in Example 7 and a nichtiönogenes surfactant.

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2553B58

Example 4

Parts by weight

Iodine 0.96

tertiary amine oxide (25 percent Lö- 7,8

solution in water).

C ₁₂ H ₂₅ O- (CH ₂ CH ₂ O) ₃ -SO ₃ Na 12.0 (7O percent solution in water)

Or thopho sphor acid e 0.4

Water 78.84

100.00 Free iodine: 0.64 %

Example 5

Iodine 1.25

tertiary amine oxide (25 percent Lö- 11.3

solution in water ')

Cetyltrimethylammonium chloride 41.5 (29 percent solution in water)

Orthophosphoric acid 7.5

Sulfuric acid 11.7

Water 26.75

100.00 Free ^ iodine: 0.60 %

Example 6

Iodine ■ 2.6

tertiary amine oxide (25 percent Lö- 10.7

solution in water)

C ₁₀ H ₂₁ O- (CH ₂ CH ₂ O) ₉ -H 10.7

Benzyl lauryl dimethyl ammonium chloride 41.8 (50 percent solution in water)

Orthophosphoric acid 7.5

Sulfuric acid 11.7

Water 15.0

100.0 Free iodine: 2.13 &

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Example 7

iodine

tertiary amine oxide (25 percent solution

in water)

C ₁₀ H ₂₁ O- (CH ₂ CH ₂ O) ₉ -H orthophosphoric acid

C ₁ 2 ^H 25 ° - (CH ₂ CH ₂ O) 3 SO ₃ Na

(70 percent solution in water) water

Free iodine: 0.81 %

Parts by weight

0.96 3.9

3.9 0.36 12.0

78.88

100.00

According to the procedures described above, the iodine-containing agents of Examples 4 to 7 were compared with respect to their Efficacy against S. choleraesuis and M. fortuitum investigated. Growth inhibition was given in the following Dilutions with water using 1 part of the iodine-containing agents found:

Example example example example 4 5 6 7

S. chloraesuis
M. fortuitum

1:25 1:20

1:35 1:20

1 j 80
1: 100

1/35 1:20

In Examples 8 to 14 below, the iodine-containing agents are prepared according to Example 2. The determination of the free iodine is carried out according to Example 3.

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example

Amine oxide solution according to Example ² orthophosphoric acid

2-propanol

Free iodine: 1.73 %

Dilution of the growth inhibitor

Solution with water "at S. choleraesuis 1:30

Dilution of the growth-inhibiting solution with water in the case of M. fortuitura

Parts by weight

2.45 66.0

1.75 29.8 100.00

1:80

Example 9

Pyridine-1-oxide

2-propanol

Orthophosphoric acid

water

Free iodine: 1.61 %

Dilution of the growth-inhibiting solution with water for S. choleraesuis

Dilution of the growth-inhibiting solution with water in the case of M. fortuitum 1:60

1: 100

1.66 16.6 40.0

0.5 41.24

100.00

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Example 10

O-COC ₂ H ₄ ) ₉ -H

Dimethyleocosamine Oxide (40Drozei Solution in water, Aromox DMCD Armor Hess Chemicals Ltdl)

.ae

Bis- (2-hydroxyäthyi) -cocosamine oxide (40 percent solution in water, Aromox C / 12 ^ 04 Armor Hess Chemicals Ltd.)

Orthophosphoric acid

sulfuric acid

water

Parts by weight

(A) (B) 5 5 22.5 22.5

5 _t 5 5.5 15.6

15.6

Free iodine, 56

Dilution of the growth inhibitor.

Solution with water "at S. choleraesuis 1: 200

Dilution of the growth-inhibiting solution with water in the case of M. fortuitum

9.3 9.3 15.0 15.0 27.1 27.1 100.0 100.0 (A) (B) 3.81 3.54 1: 200 1: 200 1: 120 1: 120

example

iodine 0.95 Amine oxide solution according to Example 3 7.9 Dodecyl toenzenesulfonic acid 8.4 Orthophosphoric acid 0.35 2-propanol 16.0 water 66.4

100.00

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Free iodine: 0.85 %

Dilution of the growth-inhibiting solution with water for S. choleraesuis

Dilution of the growth-inhibiting solution with water in the case of M. fortuitum

1550 1:35

example

^C 10-12 ^H 21-

Amine oxide solution according to Example 2 ttJ (5% solution) Orthophosic acid Glycerin, water

Free iodine: 2.3 %

Dilute the anti-growth solution with water at S. choleraesuis

Dilution of the growth-inhibiting solution with water in the case of M. fortuitum

Definitely share

2.5 11.3

³ > ¹ 14.4

0.4

2.4 40.0

25.9 100.0

1: 110

1: 75

example

^C 10-12 ^H 21-

Benzyldimethylamine oxide (30 percent solution in water) Orthophosphoric acid Sulfuric acid water

4.75 21.3

5.4 19.8

8.8 14.3

25.65

100.00

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Free iodine: 4.2 $ 6-

Dilution of the growth-inhibiting solution

with water at S. choleraesuis 1: 250

Dilution of the growth-inhibiting solution

with water in M. fortuitum 1: 140

Example 14

Parts by weight

Iodine. 2.85

C ₉ H ₁₉ C ₆ H ₄ O- (OC ₂ H ₄ ) ₁₂ -H 14.15

Amine oxide solution according to Example 2 \ 13.25

Orthophosphoric acid 8.0

Sulfuric acid 13.0

Water 48.75

100.00

Free iodine: 2.15 %

Dilution of the growth-inhibiting solution

with water for S. choleraesuis 1:90

Dilution of the growth-inhibiting solution

with water for M. fortuitum 1:60

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Claims (1)

P a t e η t a η S ₁ ρ r ü c fa e (1 ) Microbicidal mixtures containing iodine and at least one tertiary amine oxide. 2. Mixtures according to claim 1, characterized in that the tertiary amine oxide has the general formula I. having, in which the radical R, R 'and R are identical or different and each represents an optionally substituted, unbranched or branched alkyl or alkoxy radical, an aromatic or heterocyclic group. 3. Mixtures according to claim 2, characterized in that in of the general formula I at least one of the radicals R ^, R £ or R ^ is an optionally substituted pyridine or Represents quinoline residue. 4. Mixtures according to claim 1, characterized in that the tertiary amine oxide the general formula II (II) RliO 60982 3/0955 _ 25 - ["NAOHQEKEtCHT has, in which the radical R is an optionally substituted, represents unbranched or branched alkyl or alkoxy radical. - ■ "." ■■ 5. Mixtures according to claim 4, characterized in that the substituted R represents a C ₁₂ -> ^C 14 " ^{5 C} 16""' ^d 18 ~ / ethoxy radical. 6. Mixtures according to Claim 1, characterized in that the tertiary amine oxide is bis ~ (2-hydroxyethyl) decylamine oxide. 7. Mixtures according to claims 1 to 6, characterized in that ^ net that they are dissolved in a liquid medium that consists of Water or a monohydric, dihydric or polyhydric alcohol or mixtures of at least two of the above components consists. 8. Mixtures according to claim 7, characterized in that the liquid medium consists of glycerine or a mixture of glycerine and water. ' 9 ... Mixtures according to Claims 1 to 8, characterized in that that they are in acidic solution. 10. Mixtures according to claim 9, characterized in that they Contain sufficient acid for a 1% aqueous Solution of the mixtures has a pH of 6 or less. 609823/0955 11. Mixtures according to claim 10, characterized in that the acid content is so "dimensioned that a 1 percent aqueous LS solution of the agent has a pH of 1 Ms 4, 12. Mixtures according to Claims 9 to 11, characterized in that that they contain at least one water-soluble acid in aqueous solution. 13. Mixtures according to claim 12, characterized in that they as acid hydrochloric acid, sulfuric acid, phosphoric acid, sulfate contain minic acid, hydroxyacetic acid and / or citric acid. 14. Mixtures according to Claims 1 to 13, characterized in that that they contain at least one nonionic, anionic or cationic surfactant or mixtures thereof. 15. Mixtures according to claim 14, characterized in that they at least one cation-active and at least one non-ionic Contains surfactant. 16. Mixtures according to Claim 14, characterized in that they contain at least one nonionic and at least one anionic Contains surfactant. 17. Mixtures according to claims 14 to 16, characterized in that that the nonionic surfactant has the formula 609823/0955 C ₁₀ K ₂₁ O- (CH ₂ CH ₂ O) ₉ -H. Has. 18. Mixtures according to claims 14, 15 or 17, characterized in that that the cationic surfactant has the formula Br * 19. Mixtures according to claims 14, 16 or 17, characterized in that that the anionic surfactant has the formula Has C ₁₂ H ₂₅ O- (CH ₂ CH ₂ O) _{3 -SO 3} ITa. 20. Mixtures according to claim 14, characterized in that the surfactant by reacting an active one Organic compound containing hydrogen atom with a Alkylene oxide has been produced. 21. Mixtures according to Claims 1 Ms 20, characterized in that that they contain at least one water-soluble iodide. 809823/0955 22. Mixtures according to claim 21, characterized in that the water soluble iodide is potassium iodide. according to claim 1, characterized in that they by dissolving 3 parts by weight of iodine in 17 parts of one weight nonionic surfactants of the formula Adding the resulting solution with 5 parts by weight of a 30 to 45 percent aqueous solution of bis (2-hydroxyethyl) decylamine oxide and then acidifying the resulting product by adding a solution of 13 parts by weight of sulfuric acid and 8 parts by weight of phosphoric acid in 66 parts by weight of water. 24. Mixtures according to claim 1, characterized in that they by dissolving 3.4 parts by weight of iodine in 19 »6 parts by weight a 25 percent aqueous solution of a tertiary amine oxide of the general formula II according to claim 5? in which the remainder R predominantly has the meaning given in claim 5, adding 19.4 parts by weight of a solution to the resulting solution, nonionic surfactant of the formula and subsequent acidification of the resulting product by adding a solution of 13.3 parts by weight of sulfuric acid, 8.1 x parts by weight of phosphoric acid in 36.2 parts by weight of Was 60 9823/0955 ser have been manufactured. 25. Mixtures according to claim 1, characterized in that they by adding 100 parts by weight of the claim 24 Mixtures. labeled with 0.4 parts by weight of potassium iodide
have been manufactured. Mix 26. A process for the preparation of - according to claim 1 to 25, characterized in that one iodine in a tertiary
Brings amine oxide into solution. 27 · The method according to claim 26, characterized in that the iodine is first in a surfactant dissolves, in the resulting solution a solution of the tertiary
Amine oxide stirs in ¹ and with the solution of iodine in the surfactant mixed and the resulting product then acidified in such a way that. a 1 percent aqueous solution of the acidified product has a pH of 6 or less. 28. The method according to claim 27, characterized in that 0.5 to 20 parts by weight of iodine with 5 to 50 parts by weight of the surfactant and then the resulting solution with 1 to 30 parts by weight of the tertiary Amine oxide added. 29. The method according to claim 26, characterized in that the iodine is first dissolved in the tertiary amine oxide and the 609823/0955 resulting iodine-amine oxide solution then with a cation-active, non-ionic and / or anionic surfactant, a mixture of at least one cation-active and. at least one nonionic tens id or a mixture of at least one nonionic and at least one anionic surfactant added and the resulting product is then acidified in such a way that a 1 percent aqueous solution of the acidified Product has a pH of 6 or less. 30. "The method according to claim 29, characterized in that 0.5 Ms 20 parts by weight of iodine with 1 Ms of 50 parts by weight of the tertiary amine oxides and the resulting solution then siit 1 Ms 30 parts by weight of a surfactant or a mixture of surfactants added. 31. The method according to claims 26 "to 30, characterized in that that at least one water-soluble iodide is added to the resulting product " 32. The method according to claim 27 Ms 31 »characterized in that that the acidification is carried out by adding an aqueous solution of sulfuric acid and phosphoric acid. 33. Use of the means according to claims 1 Ms 25 as MicroMzidei 609823/0955