DE1024207B - Preservative and protective agent against the formation of microorganisms - Google Patents

Description

GERMAN

kl 3Oi 3

INTERNAT. KL. A 61 1

PATENT OFFICE

L24663IV a / 3Oi

REGISTRATION DATE: AUGUST 25, 19 54 NOTICE

DECAN-REGISTRATION Π. F β b Γ U a Γ iS5S

AND ISSUE OF THE

EDITORIAL:

It has been found that the salts of hydrazine with inorganic or organic acids of phosphorus represent valuable preservatives and protective agents against the formation of microorganisms and as such either alone or together with other known preservatives and Protective means can be used.

There are low molecular weight compounds such as hydrazine orthophosphates, hydrazine pyrophosphates or tripolyphosphates into consideration, depending on the intended use, slightly or sparingly water-soluble salts selected can be. However, the higher molecular weight hydrazine salts of polyphosphoric acids are also very suitable or metaphosphoric acids. In these compounds are the complexing properties united with the preservatives.

Of particular interest as preservatives and protective agents are the surface-active hydrazine salts, which by reacting preferably aqueous hydrazine solutions with acidic alkylphosphoric acid ao esters, alkylphosphonic acids or the like. The compounds of this type are therefore special technically valuable because, as surface-active substances, depending on the special structure, they are wetting, able to exert washing, dispersing or emulsifying effects and these properties with excellent preservation and protection against the formation of microorganisms unite. The surface-active substances of this type in the form of their alkali or ammonium salts observed favoring the spread of bacteria or harmful fungi is avoided, if these surface-active substances are wholly or only to a small extent in the form of the hydrazine compounds are present.

Sometimes it is useful to strengthen the bactericidal and fungicidal effects of the hydrazine compounds in the form of their complex or double salts with mono- or polyvalent metals, in particular Copper, mercury or chromium. Also these hydrazine heavy metal compounds can be used as salts of the low molecular weight as well as the higher molecular weight acids of phosphorus Use.

The effectiveness of hydrazine and its compounds is directed against bacteria as well as against fungal pests, in particular mold. The development of enzymes by bacteria and fungi is inhibited, as a result of which the enzymatic breakdown of cellulose materials or proteins is disturbed. Even small amounts of the hydrazine compounds counteract the development of dirt and slime bacteria. It is thus possible, for example, already by a 0.02 to 0.05 ⁰ / o solution conservation and protection against the formation of micro-organisms

Applicant:

Joh.A.Benekiser G.m.b.H., chemical "factory, Luchvigshafen / Rhine, Frankenthaler Str. 3

of dihydrazinium orthophosphate or dihydrazinium disodium pyrophosphate to suppress the formation of such microorganisms. Sometimes it is advisable to take these hydrazine salts together with others To use salts, for example with table salt. An addition of 0.5 to 2% of the aforementioned hydrazine salts to table salt significantly increases its preservative effect.

In many cases it is useful to combine the hydrazine compounds of the type described with others to use fungicidal or bactericidal substances to increase their effect. Such substances are Formaldehyde, paraldehyde, phenols and cresols, o-phenylphenol, chlorophenols and chlorocresols, chlorinated Oxydiphenylmethane derivatives, salicylic acid derivatives, such as phenyl salicylate, salicylic acid anilide, phenyl mercury compounds, Propylene glycol, cationic products such as fatty amines or quaternary ammonium bases in salt form and finally also inorganic products such as fluorides or silicon fluorides. Can be cationic preservatives generally only used together with hydrazine salts of low molecular weight acids of phosphorus Find.

A particular embodiment of the process consists in the use of hydrazine salts inorganic or organic acids of phosphorus together with surface-active compounds, which in itself have little or no preservative and protective effect against microorganisms own. Besides the already mentioned hydrazine compounds of the higher molecular weight, surface-active Type can also be low molecular weight hydrazine compounds together with all known surface-active substances Substances such as soaps, high molecular weight amino acids (protein degradation products), fatty acid condensation products, Alkyl sulfates, alkyl sulfonates,

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Alkylbenzenesulfonates, sulfosuccinic acid esters, etc. and the nonionic alkylene oxide adducts can be combined, especially since these compounds are often used for purposes for which a fungicidal and bactericidal effect is also desired.

The main areas of use for the hydrazine salts described, alone or in admixture with others Preservatives and / or surfactants include the preservation of solutions, slurries, jellies and pastes organic colloids. For example, an addition of 0.1 to 0.5% of dihydrazinium orthophosphate is sufficient or pentahydrazinium tripolyphosphate entirely to preserve a 3% gelatin jelly.

Such preparations are widely used in industry, for example in Production of binders and adhesives, for printing materials, thickeners, paints, dye suspensions, Inks and cosmetic preparations of various kinds. Be special Solutions, slurries, jellies and pastes protected against attack by microorganisms, which contain carbohydrates and / or proteins.

Another area of application for preservatives and protective agents based on hydrazine salts of the inorganic or organic acids of phosphorus is the preservation of inorganic ones Construction materials. Especially those building materials which are exposed to unfavorable humidity and heat conditions for example, are easily subject to fungal attack indoors, can through Hydrazine salts of the type described above or also by subsequent impregnation with their solutions or, finally, can be effectively protected by paints containing these compounds.

The hydrazine salts of the inorganic or organic acids of phosphorus can be used as such or used in a mixture with other salts or inert substances as well as in solutions or suspensions will. Apart from water or the preparations to be preserved, mostly water-based preparations, are suitable many organic solvents, such as monohydric and polyhydric alcohols, hydrogenated phenols, ketones, dioxane, Polyglycols, glycol ethers and also hydrocarbons are good solvents and dispersants for these hydrazine salts or their mixtures with other fungicidal or bactericidal substances.

Hydrazine hydrate, organically substituted hydrazines and hydrazine sulfate have already become known as agents with bactericidal or fungicidal properties. Protection for these compounds as preservatives and protective agents against the formation of microorganisms is therefore not claimed here. Although hydrazine hydrate has bactericidal and fungicidal effects, this compound is highly toxic and, as a free base, is also very reactive, alkaline and therefore often unsuitable. The substituted hydrazines are comparatively difficult to prepare and often unsuitable as salt formers for the acids of phosphorus. Hydrazine sulfate differs from the above-described inorganic or organic hydrazine salts of the acids of phosphorus in that it reacts strongly in acidic form. A O, 5 ° / o solution of N ₂ H ₄ ■ H ₂ SO ₄ shows at the glass electrode a _pH value of 1.6, while (N ₂ H ₄ J ₂ -H ₃ PO ₄ at the same concentration a p _H value results. 7.3 the p _H values O, 5 ° / cent solutions of hydrazine Alkylpolyphosphaten give p _H values from 7.2 to 7.5. the virtually neutral reaction of the hydrazine salts of inorganic and organic acids of phosphorus in connection with their superior bactericidal and fungicidal effects enable these new preservatives and protective agents to be used far more widely than is possible for hydrazine sulfate Plants, fruits or the like can be treated with the solutions or preparations of these compounds without endangering them.

Claims (8)

Patent claims: 1. Preservatives and protective agents against the formation of microorganisms, containing salts of the hydrazine of the inorganic or organic acids of phosphorus. 2. Preservative and protective agent according to claim 1, containing hydrazine orthophosphates. 3. Preservative and protective agent according to claim 1, containing condensed hydrazine salts Phosphoric acids. 4. Preservative and protective agent according to claim 1, containing higher molecular organic Hydrazine alkyl phosphates. 5. Preservative and protective agent according to claim 1, containing higher molecular organic Hydrazine alkyl phosphonates. 6. Preservative and protective agent according to claim 1 to 5, containing hydrazinium phosphates as complex or double salts with polyvalent metals. 7. Preservative and protective agent according to claim 1 to 6, containing mixtures of the hydrazine salts the inorganic or organic acids of phosphorus with known preservatives and protective agents against microorganisms. 8. Preservation and protection agent according to claim 1 to 7, characterized by the simultaneous Presence of surface-active compounds, which per se have little or no Have a preservative and protective effect against microorganisms. Publications considered: Kirk-Othmer, Encyclopedia of Chemical Technologie, Vol. 7, p. 575; Audrieth, Chemistry of Hydrazine, 1951, p. 229; Chem. Abstr., 46, 275d, 1952.