SE440846B - STOREABLE SOLID MIXTURE WHEN DISSOLVING IN THE WATER PROVIDES A STRONG ANTI-MICROBIAL SOLUTION - Google Patents

Description

From German Patent Specification 807 122 it is previously known to fuse non-toxic esmerav of p-oxylbenzoic acid with sodium perborate or sodium percarbonate, to pulverize. the melt after cooling and dissolving the powder in water, the solution obtained being said to show a better disinfecting effect than a solution of p-oxybenzoic acid alone. However, the fusion of these components means a considerable thermal load on the system and leads to side reactions in which by-products occur which are not desirable in a disinfectant. In addition, the fusion of inorganic H 2 O 2 cleavers with organic materials is by no means harmless.

The object of the present invention is to provide an easy-to-prepare mixture in the form of a storable solid composition which, when dissolved in water immediately before giving, gives a solution with a high percarboxylic acid content and a good disinfectant effect. The solution can be given an alkaline reaction, which for many purposes is, in addition to the disinfection effect, sought after by the purification effect promoted by an alkaline environment.

The object is solved according to the invention by means of a storable solid mixture which, when dissolved in water, gives a strong antimicrobial solution and is based on a) derivatives of aromatic oxicarboxylic acids and b) H 2 O 2 cleavers. Inert additives may also be included.

The mixture has the characteristics indicated in the characterizing part of the main claim.

During the dissolution of this mixture and even some time after a clear solution has formed, a reaction apparently takes place between the acyloxycarboxylic acid and the hydrogen peroxide in such a way that free hydroxycarboxylic acid and peracid are formed during cleavage of the ester bond and in the alkaline solution a longer time is maintained. a certain peracid content, which could not be maintained for a comparable time when dissolving peracid alone. It seems to be essential that the ester cleavage does not take place spontaneously but requires a certain time and thus produces a high peracid content for a longer time; If, on the other hand, the individual components formed in the solution according to the invention, i.e. the peracid and the aromatic hydroxycarboxylic acid, were to be combined with each other, but would not obtain a storage-stable product either in or in form, especially not in the blends according to the invention are reduced in the range from 4 to 12. The blends according to the invention and the solutions which can be obtained by them thus do not have a combination of the individual components formed upon dissolution of the blend.

The mixtures according to the invention dissolve particularly rapidly when water-soluble salts of the aromatic eoyloxycarboxylic acid are used. The aromatic acyloicarboxylic acids or their salts and the S2 O2 cleavages contained in this mixture are not so prone that they react with each other already in the solid state, are sufficiently reactive to be dissolved in water or water. aqueous systems are immediately converted to fast-acting, mold-efficient pereyre and to hydroxycarbaxylic acid with antimicrotial long-term action.

The cleavage of the ester bond is favored by an alkaline medium.

Particularly suitable is the pH range 8-12, which is also optimal for a purifying effect of the mixture according to the invention.

However, the proportion of alkelically reacting constituents in the mixture is also adjusted so that after the cleavage of the ester the alkelicic constituents are consumed by centralization of the peracid and the new rexicarboxylic acid and thus a neutral solution is formed. Ke6 "nentf; 1 reading" here refers to a solution with a pH value from 4 to P. Bette pH «range is more favorable than an electric calyx; É» range: is the resistance of the crgenic peracids.

In the nronatic aerloxyacrylic acids used according to the invention, R may suitably be methyl, ethyl, hydroxymethyl, acetylmethyl, methoxymethyl, ethoxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-carboxyethyl, 3-earboxypropyl «, 3-carhoxy-2-oxe-prepyl-, chlor-methyl-, phenyl-, 2-methyl-phenyl-, 3-methyl-phenyl-, 4-methyl-phenyl-, 2-tert-butylphenyl-, 3-tert-butyl-phenyl-, 1-tert-tutyl-phenyl-, 2-methoxyphenyl-, 3-methoxy-phenyl-, d-methoxy-phenyl-, 2-ethylene-1Le * ;. ~ f 3 »ethoxy-phenyl-, 1- ethoxyphenyl-, 2-chloro-enyl ~, 3-% lorïen¿l ~, 4-% lorïe.¿l ~, 2-nydroïïïenyl «, 3 ~ nydroxyiienyl- oem 4» ny3roxiienylgrd; g, -. -'i, ï; fl @ vššššš fl ïš <2% !; g ¥ ÉïrY. "*"? " 1 I A109? water-soluble salts of the aromatic acyloxycarboxylic acids are lithium, sodium, potassium, ammonium and magnesium salts, wherein 1, 2, 3 or even all 4 hydrogen atoms in the ammonium cation may be substituted by alkyl radicals. Sodium, potassium, ammonium and substituted ammonium salts are preferably used.

Examples of aromatic ecyloxycarboxylic acids which can be used according to the invention are ethyl, propioryl, benzoyl-9 (4-methylbenzyl) -, (3-chlorobenoyl} -: (4-tert-butylLeneoyl) - and (4-ethylbenzo; ; 1-acid, 3-acetoxy-, 3-propionyloxy-, 3-benzoyllo-, 3- (1-; ethylbenzo; 1-oxy) -, 3- (3-chlorobenzoyloxy) -, 3- (4- tert.benzylEnsogloxy) - ooh 3- (4-methylbenzoyloxy) -benzoic acid sent 4-acetoxy-, 4-yryoenyloxy-, β-benzoyloxy-, 4- (4-methylobenzyoyloxy) -, 4- (3-chlorobenzoyloxy) - , 4- (4-cert. Butylbenzoyloxy) - and 4- (4-methylbenzoyloxy) -benzoic acid, in addition to which acetyl, benzoyl, (4-methylbenzoyl) and (4-tert-butylbenzoyl) are preferred. salicylic acid, 3-acetoxy-, 3-benzoyloxy- and 3- (4-methoxybenzoyloxy) -benzoic acid and 4-acetoxy-, 4-propionyloxy-, 4-benzyloxy- and 4- (4-methoxy-benzoyloxy) -benzoic acid.

As H2C2 cleavers for the purposes of the invention, it is convenient to use alkali perborates, alkali metal carbonates, alkali metal periosates, alkali metal oxides, alkali salts of Caros reegens, alkali metal elements of peroxide sulfuric acid and per urea, the electrolytic salts of sodium, calcium salts; and nnnoniun.

The water-soluble salts of the aromatic acyloxycarboxylic acids contained in the mixtures according to the invention have high solubility and low solubility in water, are easy to frame and have a higher melting point than the acid on which it is based.

This high melting point is of particular importance for practical use. Otherwise, a lump formation in the blend could occur during storage, for example by solar irradiation or storage at high temperature. The sodium melt of benzoylsalicylic acid, for example, has a melting point above 300 ° C. Thus, the salts of the aromatic ecyloxycarboxylic acids ideally eliminate the need for trouble-free storage without clumping, which would have a very favorable effect on a rapid and uniform solution of the mixture according to the invention in water or aqueous systems.

The organic peracid formed during dissolution has a prominent, very rapidly occurring antimicrobial effect. This immediately occurring microbicidal action of the peracid is very important for the practical use of the mixtures according to the invention eooneirnnrfïf t771447s-1 substances to oxygen on the basis of the kerboxylic acid or other catalytic action. w-.I TEL; Of particular importance for the practical use of the mixtures according to the invention is furthermore that the second fmmyonent in the ester cleavage, i.e. the aromatic hydroxycarboxylic acid itself, has antimicrobial action. Deus verkningnednt can iqte ¿5niHf%; WU¿syric acid, which leads to rapid microbial killing. However, the nemxate n-J ~ J-roxicarboxylic acid exceeds the peracid in terms of time, the weight ratio of aromatic acylozycarboxylic acid cheese H2O2 «cleavers can be varied within wide limits in the blends according to the invention. Kan kan can thus use a volatile vector ratio from 1113 to 1021. The ratio is preferably between # 14 and 421.

The elixir according to the invention may also contain organoindic and inorganic salts for the adjustment and stabilization of the p-value in the solution prepared from the mixture. Such salts are, for example, alkali metal alkali phosphates, alkali metal pyrousrates, alkali metal polyphosphates, alkali metal tripolyphosphates, alkali metal carbonates, alkali metal hydrogen carbonates, alterates, alkali metal ethers, alkali metal citrates, alkali metal lactates and alkali metal phthalates. These inorganic and / or organic salts may enter; in the compositions of the invention in an amount of 1 to 93% by weight, preferably 5 to 80% by weight. Detergents can also be added, which are the form of hydration and the purifying effect of the solution produced by them.

For example, enionic detergents, namely alkyl sulphates, such as coconut fatty alkyl sulfates and tallow fatty alkyl sulfates; elkyl sululates, nasal lauryl sulionates; alkylaryleulfonates, such as alkylbenzene sulfonates, whose alkyl residues contain 8 to 14 Ceetones; soaps of natural or synthetic fatty acids; elk "letersul1ater, alrylfeno3 ~ etersnlfater and alkyl sulfosuccinates, such as leurylalfoholsulíosucci- neta and nonionic detergent substances, namely alkylfenolgušg- glycol ethers such as nonylphenol polyglycol ether, iettalkoholye1; @ ~ lyknl etrara fetteyrapolyglykolestrar; polyuxiprupylenglykcïer (Plurnnies), aminoxíder as dodeeyldimetylaminoxider and betaines, boxisnlfat or sulfonate betaines. 'in! \.' i “fl> f ~ w» - .- ,,,, ß '- «va.“ w leg-u ... -v.,.

UÉÃL * 77¶447š = l The proportion by weight of these substances in the mixture according to the invention may amount to 0.5 to 80% by weight and preferably 1 to 5% by weight.

Furthermore, substances may be included which increase the stability of the organic peracid formed during the hydrolysis, for example complexing agents, the sauce ethylenediaminetetraacetic acid and its alkali salts, nitrile triacetic acid and its alkali salts, alkali salts of metaphosphoric acid, alkali salts or pelyphospharicylic acid acids, alklylionic acids, dialkylphosphonic acids such as methylenedilosphonic acid, polyphosphonic acids, urea, pyridine-2,3-dicarboylic acid or pyridine-2,5-dicarboxylic acid.

At the same time, some of these substances have the task of binding heavy metal ions through complex formation, which can give colored monplexes with the aromatic hydroxycarboxylic acids, while others soften water by binding the alkaline earth ions that cause the hardness of the water. The substances mentioned may be included in the mixture according to the invention in an amount from 0.5 to 80% by weight and preferably from 2 to 20% by weight. Inert fillers can also be added, for example alkali metal sulphates, alkali metal chlorides, alkali metal silicates, carhoxymethylcellulose and water-soluble salts of aromatic sulphonic acids, such as benzene, toluene, xylene and cumene sulphonic acid. These substances, which may also have the task of binding water to prevent lump formation in the mixture by humidity, liberated crystal water or other sources of wheat, may be used in an amount of from 0.5 to 80% by weight and preferably from 2 to 50% by weight in the mixture.

Corrosion inhibitors, perfumes and other antimicrobially active substances can also be added, suitable corrosion inhibitors are benzotriazole, alkali phosphates, alkali hexametaphosphates, alkali nitrates, alkyl phosphates, amine oxides, ammonium soaps, sodium fluorosilicon acid, .5 to 30% by weight, preferably 1 to 20% by weight.

Suitable additional antimicrobially active substances are carboxylic acids, such as benzoic acid, salicylic acid and sorbic acid, phenols, such as 2,6-dimethyl-4-bromophenol and o-phenylphenol.

The solutions prepared by the mixtures according to the invention are suitable for disinfection and cleaning of instruments, tools, utensils, wall and floor and other surfaces in the hospital area ooh 7714473-1 -å 1äkar «and veterinary repairs§ in the household, on iydnsïriellw» L and public workplaces true inøm sanitëromršöei.

The electrical networks may be in the form of powder, frauulan, tablets or anear-shaped solid creeps. The water solutions and the water solutions produced are generally lukbírla. In addition, there is the additional advantage that the solutions are toxicologically harmless.

The antimixrobial effect nos those of the mixtures ealiït fi gp-. the findable solutions are shown in the attached tables and 2. The bacteriological examinations were carried out according to; t ri l lines are tested for chemical ñ disinfectants (DG The tables illustrate = the broad vntimicrobial fl across the spectrum, even against fungi; the long effect flfi idea fi usually a durability of about 1 äag for a disinfeätlonsläsnin fi \ N \ N PNN \ FN om N \ PNN \ «NN \. N m mN N \ ~ NN \« NN \ f N m of Hwñä fi v mr HPN \ f NN \ ~ NN \ f NN \ f N om N \ ~ NN \ ~ NN \ f NN \ f N om N \ f NN \ ~ NN \ «N _N \ f N mN Ednwm Rom + nr sr ONF A nr om AN \ ~ NN \« NN \ ~ NN \ ~ NN \ fw \ _ N \ ~ N mN NP nw A ONPA mf om AN \ «NN \« N mp N \ PNN \, NN \ FN OP r \ av amß ONPA sf omm m ~ m mf N \ ~ N m om m w fi v _ væ fl mon Møm fi Mom fl u % FL% m% m H f wnsm m% ww %% et al æoHøH nw %%% MEm al HæwHs> mwnmmw al oëwwmw msmmd fl o f wmmv al MWA OBM vm FI A OBM uømpooßä H flfi oæm. BHmmm_F¶w fi WNM no al owna mßwwohm uoæm u f m f @ Hm fifi anmm @ _FNuwonoM .wHOO w f w fiflfl .EÜOOOO 771447š = ¶ NWSC fi wønomm uo al msmææw Pm fi vmm nwpmnm fi u MmmEæ> m Nno fl møøamøm nm fl mwvxwn .mo fi m fi mmmsm www. _ Wnm fi m fl nohä fl ä ^.Pm@Nv oNm N ooN HHNN Hmæs flfi ä om n P pmnonnwmlnm mw wm w oß m ma fl Nmm fifl vwmm fl mäsmm ~ H fl mnma 7714473-1 NN ... N Nä N Nš N N \ _. N om.

N \ «NN \ ~ NN \« N Nxf N NN wm N \ f N om of H «aaNw, wf n PN \ PNN \ ~ NN \ ~ NN \ f N om N \« NN \ PNN \ «NN \« N om N \ «NN \ f NN \ ~ NN \ f N NN Esnwm om om + av so A mf av N \ ~ NN \ ~ NN \ ~ N m N \ f NN \ ~ NN \« N MN mo so A oN ~ ^ nw om N \ ~ NN \ «NNN \ ~ NN \ f NN \ ~ N or nw A sm N oN, N no om A m Nä N om A ow N m Nï N m m fl. lover Læ al w to Ho m ... d Imæv al w f æ f O fl own access Moan MoO fi äßwnu w fl wvßßm MD fiflfi w uhmo fl n fl et al ophnn .wnmm fi, MW f ow wHHw w fl wnßm no al vmHv Imna OBM [MHA Uhwm tail flfifl woæm lnomm <AEW al onmo Iono al Hae et al ævohm ... Ohm l f m f O fl m Hm al møvm lnmo fl ow HHOU mßw fi dw WÄOBO PWHPNM HwPN al mH m flfi O fl Ho fl iff o f h f mmqpm . .u .Ham fl ffm .co fi mmmmwøm Hwwnwvmmo. ⁇ 807,122 parts by weight of p-oxybenzoic acid ethyl ester and sodium perborate were melted together, the melting temperature being about 110 DEG C. During the reaction it was observed that ethanol was formed, the melt was pulverized after cooling and dissolved in water. completely slowly and not completely in water.

The antimicrobial effect was determined according to DGHM and was found to be small in comparison with the mixtures according to Tables 1 and 2.

Claims (4)

/ l 7714473-1 P a t e n t k r a v: 1. A storable solid mixture which, when dissolved in water, gives a strong antimicrobial solution and is based on a) derivatives of aromatic oxicarboxylic acids and b) HZO Splitter, and the mixture may also contain inert additives, characterized in that the mixture as a derivative of aromatic oxicarboxylic acids contains an aromatic acyloxycarboxylic acid of the general formula COOH in which R represents a low molecular weight alkyl radical which may be substituted by a hydroxy, a low molecular weight alkoxy, a low molecular weight acyloxy or a carboxy group or a halogen atom, or a phenyl group which may be substituted by hydroxy groups, halogen atoms, low molecular weight alkyl or alkoxy groups wherein the carboxyl group may be in the o-, m- or β-position to the acyloxy radical, or water-soluble alkali, alkaline earth metal or ammonium salts of the aromatic acyloxycarboxylic acid wherein up to H hydrogen atoms in ammonium catene fi enee 'of being substituted by alkyl radicals, and that the molar weight ratio of H 2 ozomicarboxylic acid splitters are between 1:10 and 10: 1. A mixture according to claim 1, characterized in that it additionally contains a stabilizer for peracids. Mixture according to Claims 1 to 2, characterized in that it contains compounds for adjusting and / or stabilizing the pH within the range. A mixture according to claims 1 to 3, characterized in that it contains detergents, corrosion inhibitors and / or water-binding agents.