DE1617238C - Detergent iodine composition - Google Patents

Description

RO - (AO, PO) _x (AO, PO) ₁ H

is shown. wherein R is a primary C ₁₄ - to C ₁₈ -alkyl radical, the proportion by weight of ethylene oxide is in the range from 0 to 45% in one of the blocks χ or y and in the range from 60 to 100% in the other of the blocks χ or y, and the total number of moles of alkoxide ranging from 6 to 40 moles, with 1 to 10 moles in the propylene oxide-rich block and 5 to 30 moles ^; M ethylene oxide-rich block lies.

2. Composition according to claim 1, characterized in that the block χ contains 0 to 45% ethylene oxide and gives 1 to 4 moles of alkoxide and the block y contains 60 to 90% Äthylenoxvd and gives 5 to 20 moles of alkoxide.

3. Composition according to claim 2, characterized in that the block contains χ 25% ethylene oxide and gives 4.3 muI alkoxide and the block y contains 75% ethylene oxide and 14.5 moles of alkoxide result and RC ₁₅ -alkyl.

German Auslegeschrift 1 660 0.Ί4 germicidal detergents are known in which the complex compounds of iodine and nonionic condensation products of ethylene oxide and a water-insoluble polyalkylene s exist. It is already pointed out there that such higher fatty alcohols with 10 to 18 carbon atoms can be used as ethylene condensation products, but there is a further one

ίο Addition of surface-active agents to the complexes of iodine and condensation products of ethylene oxide and a water-insoluble polyalkylene oxide.
US Pat. No. 2,931,777 is known.

as a detergent component of germicidal detergent-iodine compositions Polyalkylene oxide derivatives of water-insoluble aliphatic hydroxy compounds to use. However, it has been found that such detergents have a broader scope in their complexing ability for iodine "and in the properties of the resulting Deiergens iodine composition Changes in both the hydrophobic and hydrophilic components will vary.

The object of the present invention is to provide such detergent-iodine compositions, which, with full germicidal activity, have a stronger color than the known compositions and to the extent of their diminishing effect through repeated use get a lighter color, which serves as a indicator for the consumer.

The invention relates to a detergent-iodine composition containing a detergent-iodine complex, which provides a germicidally effective amount of iodine, the detergent component of the complex a water-soluble condensate of straight-chain. primary fatty alcohols with 14 to 18 carbon atoms represent with ethylene oxide (AO) and propylene oxide (PO), according to the formula

It is known that solutions of iodine, which is bound in complex with detergents. show an increased color compared to aqueous iodine solutions. Most cleaning iodine solutions are formed with a level of 25 to 75 parts per million (ppm) of available iodine. At these levels the iodine color is easy to see; Differences in coloration as a function of detergent, which can be measured instrumented, can hardly be perceived by the eye and therefore never received any attention. Dilutions in the / 2 ppm range that are used exclusively for disinfectant rinsing are only weakly colored. Since such solutions are used on clean surfaces is almost no loss of iodine by reaction with proteinaceous dirt, and therefore, the problem is the observation of the staining as a measure of when a supplement is required and is not of great importance. To the extent that improved coloration of the detergent iodine in-use dilutions can push out the range of perception of the iodine, the amounts of iodine required in the in-use dilutions for both cleaning and sanitary purposes can be safely decreased. The reason for this is that the germicidal effect of iodine is recognized in concentrations as low as fractions of a ppm.

RO - (AO, PO) ₁ (AO, PO) ₁ H

wherein R is a primary alkyl radical having 14 to 18 carbon atoms. the proportion of ethylene oxide, in percent by weight, is in the range from 0 to 45% in one of the blocks χ, y and in the range from 60 to 100% in the other of the blocks x, y , and the total number of moles of alkoxide is in the range of 6 bk 40 moles, with 1 to 10 moles in the propylene oxide-rich block and 5 to 30 moles in the ethylene oxide-rich block.

Generally preferred among the detergents described above are those in which the χ block contains 0 to 45% ethylene oxide and gives 1 to 4 moles of alkoxide, while the y block contains 60 to 90% ethylene oxide and gives 5 to 20 moles of alkoxide.

Preferred detergents of this preferred type give iodine complexes which under comparable conditions have a color intensity at 6 ppm dilution which is more than 4 times as great as with common nonylphenol-ethylene oxide-iodine complex.

In this connection it should be pointed out that such C ₁₄ - to C ₁₈ -alcohols and the detergents formed therefrom are generally not specific compounds, but mixtures which are distinguished by an average content of carbon atoms. For example, a technical C ₁₄ alcohol itself can be a mixture of two, three or more alcohols with up to ten or up to 20 or more carbon atoms in such alcohols

Amount proportions that result in an average of 14 carbon atoms for the mixture.

The water-soluble alcohol-alkylene oxide condensate, regardless of whether in the form of liquids or as waxy solid substances, can be complexed with iodine by simply increasing the detergent and elemental iodine at the appropriate Temperatures necessary to melt the waxy detergent are mixed. If the detergent is a liquid, it can complex itself by mixing at room temperature be effected, however mach »that diminished required time this is impractical.

The preferred method for preparing the complexes is the cold mixing process, as described in USA.-Patent 3 028 299, with iodine being added as an aqueous iodide-iodine solution, which is approximately 57 percent by weight I ₂ , 20 percent by weight HJ ': nd the remainder contains water. This procedure is particularly useful in the preparation of iodine complexes with waxy or solid alcohol-ethylene oxide condensation.

The detergent-iodine complexes of the present invention can be used in germicidal agents which amounts of detergent in the range of ctv .: »0.5 to 75% and of what is available Contain iodine in the range of about 0.1 to 25%. Funds that are about 1 to 15% available Iodine and 5 to 75% detergent are suitable for products that use water when applied can be thinned by the ultimate consumer. Means which are about 15 His 25% available iodine and about 60 to 75 '', contain detergent, can be used as processing concentrates. Means in which the available iodine is about 0.1 to 1.0% and which contain about 0.5 to 10% detergent can suitably directly or dilution with water can be used. In non-acidified products for general For sanitary purposes (general hygiene), the remainder of the agent can be water or a mixture of water and isopropyl alcohol. On the other hand, it is in use in the dairy industry and in others Applications where excessive !. Amounts of organic pollution may be present, preferable than additional components to use a mixture of water with compatible acids.

When compositions are prepared by the cold method using the above-mentioned aqueous HI iodine solution, the composition also contains about 1 part 3 for every 3 parts I ₂ . So contains e \; Agent that has 1.5% I ₂ , about 0.5% J. This "built-in" indicator is an important advantage of the new agents, which can be used with typical application dilutions of 25, 12.5 and especially 6 ppm. It is common practice to advise consumers that use dilutions should be discarded when the characteristic iodine color has disappeared. With many available agents, however, the color becomes so weak at dilutions of only 10 to 15 ρρ.η that the determination of the end product is difficult. Such application dilutions are often discarded when 50 to 75% of their germicidal activity has remained unused. Any tightening of the endpoint by providing greater color intensity at the lower application dilutions is therefore of considerable economic importance as it enables the consumer to perceive a greater disinfectant value from a given amount of detergent-iodine composition.

The color-improving effect of the condensates of primary C ₁₂ - to C _lg -alcohols with ethylene oxide does not seem to be changed very much by moderate changes in the ethylene oxide content. As already mentioned, the ethylene oxide resp.

ίο Propylene oxide supplied number of carbon atoms be about the same as or greater than the number of carbon atoms in the alcohol.

The increase in the proportion of detergent to iodine results in a marked improvement in the color intensity with low usage dilutions. Taking the detergent to iodine ratio of 5: 1 changed to 10: 1, the color intensity is generally doubled. This is special Significance in view of the fact that it is recommended for compositions with hygienic Applications below the 25 ppm iodine content is appropriate, increasingly higher ratios of Detergent to iodine to apply in order to ensure an effective amount of detergent in the more dilute use solutions to care.

As a means of reliably recording and comparing the color in detergent-iodine solutions the use of an instrument such as a Beckman spectrophotometer comes in handy. The color will measured by means of absorbance, a decimal value known as

log " , ie log ^

incident light
failed light

for a 1 cm spectrophotometer sample cell is defined.

An effective measure of the iodine that complexes in the new detergent-iodine compositions is the partition coefficient (D.C). determined in a two-phase aqueous heptane system according to the procedure described in the US Pat. No. 3,028,229 mentioned above. Surprisingly, a number of the new compositions in which iodine is associated with a primary C ₁₄ -C 12 alcohol-alkylene oxide coridensate complex show considerably higher D C values than similar compositions which contain the common nonylphenol-ethylene oxide condensate.

Finally, as standard when evaluating the new compositions, the cloud point must also be taken into account. This is the temperature above which detergents and detergent-iodine complexes in aqueous solution change from clear or transparent solutions to cloudy solutions or suspensions. In general, should the cloud point of liquid germicidal products or concentrates to be at least 50 ⁰ C and preferably above about 55 ° C, so that such products under all normal storage conditions remain clear and transparent.

Moreover, the modified detergents in liquid form can be, even if the average number of Kohlensloffatome in the radical R is up to C _{10 degrees.} These factors are of critical advantage in the preparation and use of germicidal detergent-iodine compositions.

example

a) A number of detergent iodine preparations are made from iodine iodide using various condensates of primary alcohol in the C ₁₄ to C _1K range and ethylene oxide alone. These preparations are aqueous solutions containing 10 percent by weight detergent. Contain 1 percent by weight of available iodine and 0.35 percent by weight of iodide, the iodine and iodide being supplied as a HJ iodide solution with a content of 57% available iodine and 20% HJ.

In Table A, the detergents are represented by the number of carbon atoms in the primary alcohol component, the number of moles of condensed ethylene oxide, the cloud point of a 1% aqueous Solution and physical state at 25 C identified. For the detergent-iodine compositions obtained are values for the distribution coefficient (D. C), determined by the formula:

mg of I in the aqueous phase, ml of heptane

'' ~, ng J in heptane ml aqueous phase

specified.

In addition, the relative color of dilute solutions with concentrations of available iodine of 25, 12.5 and 6 ppm, together with the wavelength in my. the peak position or maximum absorption for the 25 ppm solution. The relative color or absorption refers to log 'j for the unit path length, where / ₀ and / are "incident light" and "emergent light", respectively. A Beckman-Du spectrophotometer with cells of 1.00 cm path length was used.

Table A.

sample C-Alome Mole Cloudy Phys. Zusiand D C Relatn e color lAbsorplioni 6 ppm No. AlhO Point at 25 C 0.065 C. 25 ppm __ 12.'S ppm 1 . 14 Φ 8.5 65 fluid 100 0.800 0.245 0.060 (12 to 20) 1 14 0 7.5 61 fluid 96 0.735 0.220 0.060 (12 to 18) 3 14 0 8.1 65 fluid 102 0.795 0.240 0.090 (12 to 18) 0.085 4th 14th 7.6 63 fluid 86 0.900 0.310 0.090 5 14th 9.2 82 fixed 95 0.885 0.300 ■ 0.070 6th 16 7.4 __ fixed 103 0.790 0.275 0.065 7th 16 10 76 fixed 127 0.720 0.245 0.080 8th 16 20th > 100 fixed 107 0.705 0.240 0.105 9 18th 10 68 fixed 86 0.670 0.240 10 18th 20th > 100 fixed 76 0.820 0.300

25 ppm peak

390 385 390

385 385 385 385 385 390 390

b) In the same way as described under a), become aqueous; Detergent-iodine solutions prepared as detergent components condensates of primary alcohols in the C ₁₄ - to C ₁₈ range with mixtures of ethylene oxide and propylene oxide in the invention, by the formula

RO- (AO, PO) YES O, Ρ0), Η
contain certain ratio:

Detergent C atoms
in R Weight percent AO in »> '« MoIAO
+ PO Moles of AO
+ PO in ".ν" 75 in ".τ" in "y" C. 15th 25th 85 4.3 14.6 d ! 4 15th 70 3.9 14.0 e 14th 30th 70 4.0 13.5 f 14th 30th 2.4 10.8

Detergent C atoms
in R Weight percent AO in "y" Moles of AO
+ PO Moles of AO
+ PO in ".v" 75 in "x" in ny « a 14th 25th 25th 4.0 13.7 b 14th 75 13.7 4.0

The detergents and the aqueous solutions of their iodine complexes are tested as in Example 1, and the results are summarized below:

Table B.

sample

Detergent

Cloud point
° C

64
64

physical condition
25 ^ C

fluid
fluid

D. C.

75
70 Aqueous Complex

relative color (absorption)

25 ppm 1 2.5 ppm 6 ppm

0.880 0.295 0.080

0.870 0.275 0.070

25 ppm peak

(ΓΠμ)

390

Del
Triibungspunkl 7th 1,617,238 r 8th continuation Aqueous complex
relative color (absorption) 25 ppm 12.5 ppm 6 ppm 25 ppm peak C. DC. 1,045 0.355 0.110 <m _: i) sample 65 crgcns
physical condition 0.940 0.315 0.085 390 73 25 C 92 0.890 0.295 0.085 390 'C 58 fluid 70 0.905 0.290 0.075 390 d 55 fluid 75 390 e fluid 70 r fluid

It is characterized by the finding that samples a to fine are markedly better in color at the three dilutions result as the corresponding samples mentioned under a) on the basis of its ethylene oxide / alcohol condensates. Sample c, the best representative in Table B., provides color values for each of the three dilutions that are at least 10% better than that of the best representative, sample 4, from Table A.

Claims (1)

Patent claims: 1. Detergent-iodine complex containing a detergent-iodine complex. the one germicid provides an effective amount of iodine, the detergent component of the complex being a water-soluble Alkylene oxide is condensate and the ratio of delergent to available Iodine in the complex is at least 3: i, characterized in that the detergent component of the complex is a condensate of primary alcohol and alkylene oxide. that by the formula